TWI525140B - A complex composition including an inorganic oxide particle and a silicone resin, and a transparent composite - Google Patents

A complex composition including an inorganic oxide particle and a silicone resin, and a transparent composite Download PDF

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TWI525140B
TWI525140B TW101106487A TW101106487A TWI525140B TW I525140 B TWI525140 B TW I525140B TW 101106487 A TW101106487 A TW 101106487A TW 101106487 A TW101106487 A TW 101106487A TW I525140 B TWI525140 B TW I525140B
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inorganic oxide
resin
oxide particles
polyfluorene
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TW201249910A (en
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大塚剛史
佐藤洋一
栗野恭行
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住友大阪水泥股份有限公司
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

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Description

無機氧化物粒子與聚矽氧樹脂之複合組成物及透明複合體 Composite composition of inorganic oxide particles and polyoxynoxy resin and transparent composite

本發明係有關無機氧化物粒子與聚矽氧樹脂(silicone resin)之複合組成物及透明複合體。 The present invention relates to a composite composition of an inorganic oxide particle and a silicone resin and a transparent composite.

本申請案是根據於2011年6月8日在日本提出申請之特願2011-128302號申請案而主張優先權，在此援用其內容。 The present application claims priority based on Japanese Patent Application No. 2011-128302, filed on Jan.

以往，嘗試將二氧化矽等無機氧化物當作填充劑並與樹脂進行複合化，藉以提高樹脂之機械特性等。使此填充劑與樹脂複合之方法，一般而言是將無機氧化物分散於含有水及有機溶劑之任一方或雙方的溶液中而製成分散液，並將該分散液與樹脂混合之方法。將分散液與樹脂經由各種方法混合，可製作以無機氧化物粒子當作第2相而複合成的無機氧化物粒子複合塑膠(例如參照專利文獻1)。 Conventionally, an inorganic oxide such as cerium oxide has been attempted as a filler and composited with a resin to improve the mechanical properties of the resin. The method of combining the filler with the resin is generally a method in which an inorganic oxide is dispersed in a solution containing either or both of water and an organic solvent to prepare a dispersion, and the dispersion is mixed with a resin. By mixing the dispersion liquid and the resin by various methods, an inorganic oxide particle composite plastic in which inorganic oxide particles are used as the second phase can be produced (for example, see Patent Document 1).

又，已提議藉由在無機氧化物粒子的表面被覆聚合物，而調整機械特性及折射率或透明性等適合光學特性的塗佈組成物、塗膜(例如參照專利文獻2)。 In addition, it has been proposed to coat a coating composition on a surface of an inorganic oxide particle, and to adjust a coating composition and a coating film suitable for optical properties such as mechanical properties, refractive index, and transparency (see, for example, Patent Document 2).

聚合物材料中，由於聚矽氧樹脂之耐熱性、耐寒性等耐候性優良，並且電氣特性、低毒性等也優良，故從化妝品材料或醫用材料至電氣電子材料為止，可廣範圍地使用。又，近年來，亦著眼於其透明性方面，也用於發光二極體的透明密封材料等要求透明性之構件中。 Among the polymer materials, since the polyoxyxene resin is excellent in weather resistance such as heat resistance and cold resistance, and is excellent in electrical properties and low toxicity, it can be widely used from cosmetic materials or medical materials to electrical and electronic materials. . In addition, in recent years, attention has been paid to the transparency, and it is also used for a member requiring transparency such as a transparent sealing material for a light-emitting diode.

在如此之用途中所要求的特性，可列舉：透明性、折 射率等光學特性、硬度等機械特性、耐熱性等熱安定性、抑制水蒸氣或各種氣體之穿透性的氣體阻隔性。 The characteristics required in such applications can be listed as: transparency, folding Thermal stability such as optical properties such as optical properties, mechanical properties such as hardness, heat stability, and gas barrier properties against water vapor or penetration of various gases.

以往所提案的藉由將聚矽氧樹脂與無機氧化物等無機材料複合而使光學特性或熱安定性提高者，已有如下述之多數提案：將氧化鋯粒子在螯合劑存在下與含有羥基的聚矽氧烷(polysiloxane)複合而成之組成物(專利文獻3)；將氧化鋯粒子與多官能聚矽氧烷複合而成之發光元件塗佈用組成物(專利文獻4)；將無機奈米粒子經有機化合物被覆後，混合至含有苯基的聚矽氧(silicone)中而成之發光元件用充填材料(專利文獻5)等。 Conventionally proposed, by combining a polyfluorene oxide resin with an inorganic material such as an inorganic oxide to improve optical properties or thermal stability, there have been many proposals for zirconia particles in the presence of a chelating agent and hydroxyl groups. A composition in which a polysiloxane is compounded (Patent Document 3); a composition for coating a light-emitting element obtained by combining zirconia particles and a polyfunctional polyoxyalkylene (Patent Document 4); A filler for a light-emitting element (Patent Document 5) obtained by coating a nano-particle with an organic compound and then mixing it into a phenyl-containing polysilicon.

[先前技術文獻] [Previous Technical Literature] (專利文獻) (Patent Literature)

專利文獻1：日本特開2005-161111號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2005-161111

專利文獻2：日本特開2003-292826號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2003-292826

專利文獻3：日本特開2006-316264號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2006-316264

專利文獻4：日本特開2009-91380號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2009-91380

專利文獻5：日本特開2007-70603號公報 Patent Document 5: Japanese Laid-Open Patent Publication No. 2007-70603

然而，以往，當欲將無機氧化物粒子與疏水性樹脂複合時，由於該無機氧化物粒子的表面是親水性，故尤其是在疏水性高的聚矽氧樹脂與無機氧化物粒子之間，聚矽氧樹脂與無機氧化物粒子會分離，而有難以複合之問題。 However, conventionally, when inorganic oxide particles are to be combined with a hydrophobic resin, since the surface of the inorganic oxide particles is hydrophilic, it is particularly between a highly hydrophobic polyoxynoxide resin and inorganic oxide particles. The polyoxynene resin and the inorganic oxide particles are separated, and there is a problem that it is difficult to recombine.

在此，一般之解決方法，是為了使無機氧化物粒子之 表面進行疏水化，而在無機氧化物粒子之表面賦予有機高分子分散劑等表面修飾劑，使聚矽氧樹脂與無機氧化物粒子的相溶性提高。但是，要將無機氧化物粒子之表面進行充分之疏水化而使其與聚矽氧樹脂逹到相溶為止，係屬困難，而有問題。 Here, the general solution is to make inorganic oxide particles The surface is hydrophobized, and a surface modifier such as an organic polymer dispersant is applied to the surface of the inorganic oxide particles to improve the compatibility between the polyoxynoxide resin and the inorganic oxide particles. However, it is difficult to sufficiently hydrophobize the surface of the inorganic oxide particles to be compatible with the polyoxymethylene resin, which is problematic.

又，無機氧化物粒子之粒徑為20nm以上而為大，故透明性會下降，依情況之不同，甚至會有失去透明性之問題。 Further, since the particle diameter of the inorganic oxide particles is 20 nm or more and large, the transparency is lowered, and depending on the case, there is a problem that transparency is lost.

又，例如在高黏性聚矽氧樹脂中，即使使用以往的疏水性高分子分散劑，仍難以與無機氧化物粒子相溶，即便可將無機氧化物粒子之表面充分地疏水化，仍有無法得到無機氧化物粒子之透明分散液的問題。 Further, for example, in the highly viscous polyoxynoxy resin, even if a conventional hydrophobic polymer dispersant is used, it is difficult to be compatible with the inorganic oxide particles, and even if the surface of the inorganic oxide particles is sufficiently hydrophobized, The problem of a transparent dispersion of inorganic oxide particles cannot be obtained.

又，當使用含有羥基之聚矽氧烷時，伴隨著交聯之進行而會產生水，依情形之不同，有無機氧化物粒子與聚矽氧烷會相分離之虞，再者，在所得之複合體中會有發生孔洞(pore)或碎裂(crack)之虞的問題。 Further, when a polyoxyalkylene having a hydroxyl group is used, water is generated accompanying the progress of crosslinking, and depending on the case, the inorganic oxide particles and the polyoxyalkylene are separated, and further, There is a problem that a hole or a crack occurs in the composite.

另一方面，當使用多官能聚矽氧烷時，在無機氧化物粒子與聚矽氧烷之調配上也有所限制，尤其是在無機氧化物粒子量多時，會有孔洞或碎裂之發生變顯著之問題。當使用多官能聚矽氧烷時，未反應之官能基容易殘留，而使交聯後之複合體特性容易發生經時性的變化，更進一步，導致有耐久性差之問題。 On the other hand, when a polyfunctional polyoxyalkylene is used, there is also a limitation in the formulation of the inorganic oxide particles and the polyoxyalkylene, especially when the amount of the inorganic oxide particles is large, there is a possibility of occurrence of voids or chipping. A significant problem. When a polyfunctional polyoxyalkylene is used, the unreacted functional group is liable to remain, and the properties of the composite after crosslinking are likely to change with time, and further, there is a problem of poor durability.

又，當使用螯合劑使無機氧化物粒子與聚矽氧樹脂相溶化時，因為經時性變化或熱劣化而有呈現著色之問題。 Further, when a chelating agent is used to dissolve the inorganic oxide particles and the polyfluorene oxide resin, there is a problem of coloring due to temporal change or thermal deterioration.

又，在高折射率之發光元件用充填材料中，雖提案在 容易與各種有機分子相互作用的甲基苯基聚矽氧中分散奈米粒子而成之透明分散液，但仍無法達到在低極性之二甲基聚矽氧樹脂中的透明分散及硬化體。 Moreover, in the filling material for a light-emitting element having a high refractive index, it is proposed A transparent dispersion of nanoparticles dispersed in methylphenyl polyfluorene which is easily interacted with various organic molecules, but it is still unable to achieve transparent dispersion and hardening in a low-polarity dimethylpolyoxide resin.

又，當使用加成反應型之二甲基聚矽氧時，雖會透明分散於硬化前之聚矽氧中，但在硬化步驟中，會發生相分離而有導致白化的情形之問題。 Further, when an addition reaction type dimethylpolyphosphonium is used, it is transparently dispersed in the polyfluorene oxygen before curing, but in the hardening step, phase separation occurs and whitening occurs.

另一方面，雖亦提案以往的將金屬氧化物粒子之表面以改質聚矽氧進行處理之方法，但一般因為改質聚矽氧為多官能，故無法確實處理無機氧化物粒子之表面，而有未反應之改質部位會對與聚矽氧樹脂的相溶造成不好影響之問題。於是，為了解決此問題，而嘗試實施二次或三次的表面處理(表面修飾)等來改善，但有步驟煩雜等之問題。 On the other hand, although a conventional method of treating the surface of the metal oxide particles with modified polyfluorene oxygen has been proposed, generally, since the modified polyfluorene oxide is polyfunctional, the surface of the inorganic oxide particles cannot be reliably treated. However, there is a problem that the unreacted modified portion has a bad influence on the compatibility with the polyoxynene resin. Then, in order to solve this problem, it is attempted to perform secondary or tertiary surface treatment (surface modification) or the like to improve, but there are problems such as troublesome steps.

本發明是為了解決上述課題而作成的發明。其目的是提供一種無機氧化物粒子與聚矽氧樹脂之複合組成物及透明複合體，其中，在使可提升折射率、機械特性、及氣體阻隔性且同時可維持透明性的無機氧化物粒子分散於聚矽氧樹脂中時，係為分散性高，並且，可防止硬化時的相分離/白化。 The present invention has been made to solve the above problems. The object of the present invention is to provide a composite composition of an inorganic oxide particle and a polyoxyxylene resin, and a transparent composite in which an inorganic oxide particle capable of improving refractive index, mechanical properties, and gas barrier properties while maintaining transparency is provided. When dispersed in a polysiloxane resin, it is highly dispersible, and phase separation/whitening at the time of hardening can be prevented.

本發明人等為了解決上述課題經過精心再三研究，結果發現，將平均分散粒徑為1nm以上且20nm以下之無機氧化物粒子，使用單邊末端具有1個官能基之聚二甲基矽氧烷(polydimethylsiloxane)骨幹聚合物來進行表面修飾，更進一步，使用聚矽氧樹脂與反應觸媒進行複合化，而將 無機氧化物粒子分散到聚矽氧樹脂中時，可大幅度地提高無機氧化物粒子之分散性，同時可獲得維持透明性並維持聚矽氧樹脂之耐熱性及耐光性且控制折射率的透明複合體，遂而完成本發明。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less are polydimethyl methoxyoxane having one functional group at one terminal. (polydimethylsiloxane) a backbone polymer for surface modification, and further, using a polyoxyl resin to complex with a reaction catalyst, When the inorganic oxide particles are dispersed in the polyoxynoxide resin, the dispersibility of the inorganic oxide particles can be greatly improved, and transparency which maintains transparency and maintains heat resistance and light resistance of the polyoxynoxy resin and controls the refractive index can be obtained. The composite, the present invention, is completed.

亦即，本發明的無機氧化物粒子與聚矽氧樹脂的複合組成物，其特徵是其為至少含有無機氧化物粒子、聚矽氧樹脂與反應觸媒的複合組成物；其中，無機氧化物粒子是藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾，同時平均分散粒徑為1nm以上且20nm以下之無機氧化物粒子；前述聚矽氧樹脂含有乙烯基改質聚矽氧及氫改質聚矽氧；前述反應觸媒含有矽氫化(hydrosilylation)反應觸媒。 That is, the composite composition of the inorganic oxide particles and the polyfluorene oxide resin of the present invention is characterized in that it is a composite composition containing at least inorganic oxide particles, a polyfluorene oxide resin and a reaction catalyst; The particles are surface-modified by combining a polydimethyl methoxy oxane backbone polymer having a functional group at one end, and an inorganic oxide particle having an average dispersed particle diameter of 1 nm or more and 20 nm or less; The resin contains vinyl modified polyfluorene oxide and hydrogen modified polyfluorene oxygen; the aforementioned reaction catalyst contains a hydrosilylation reaction catalyst.

前述聚二甲基矽氧烷骨幹聚合物，係以單縮水甘油基醚(monoglycidyl ether)末端聚二甲基矽氧烷及/或單羥基醚末端聚二甲基矽氧烷為佳。 The polydimethyl methoxy siloxane backbone polymer is preferably a monoglycidyl ether terminal polydimethyl siloxane and/or a monohydroxy ether terminal polydimethyl siloxane.

前述乙烯基改質聚矽氧，係以選自由兩末端乙烯基-二甲基聚矽氧、兩末端乙烯基二苯基-二甲基聚矽氧、兩末端乙烯基-苯基甲基聚矽氧、兩末端乙烯基-二乙基聚矽氧、側鏈乙烯基-二甲基聚矽氧、乙烯基甲基聚矽氧、乙烯基甲氧基聚矽氧、乙烯基樹脂分散物所成群組中之1種或2種以上為佳。 The aforementioned vinyl modified polyfluorene is selected from the group consisting of vinyl-dimethylpolyoxy at the two ends, vinyl diphenyl-dimethylpolyoxy at the two ends, and vinyl-phenylmethyl polymerization at both ends. Oxide, two-terminal vinyl-diethylpolyfluorene, side chain vinyl-dimethylpolyoxyl, vinylmethylpolyoxyl, vinylmethoxypolyoxyl, vinyl resin dispersion One or two or more of the groups are preferred.

前述氫改質聚矽氧，係以選自由兩末端氫-二甲基聚矽氧、甲基氫-二甲基聚矽氧、甲基氫聚矽氧、乙基氫聚矽氧、甲基氫-苯基甲基聚矽氧、氫化物樹脂(hydride resin)所 成群組中之1種或2種以上為佳。 The hydrogen-modified polyfluorene is selected from the group consisting of hydrogen-dimethyl polyfluorene at the two ends, methyl hydrogen-dimethyl polyfluorene oxide, methyl hydrogen polyoxymethylene, ethyl hydrogen polyoxymethylene, methyl Hydrogen-phenylmethyl polyfluorene, hydride resin One or two or more of the groups are preferred.

前述氫改質聚矽氧含有下述式(1)所示之側鏈氫改質聚矽氧： (惟，R1至R8是相互獨立的任意有機基(H除外)，m是1以上之整數，n是包含0的正整數)前述側鏈氫改質聚矽氧中，m與n之比(m/(m+n))是以0.25以上且1以下為佳。 The hydrogen-modified polyfluorene oxygen contains a side chain hydrogen-modified polyoxane represented by the following formula (1): (However, R 1 to R 8 are independently of each other any organic groups (except H), m is an integer of 1, n is a positive integer including 0) is the hydrogen side chain modified poly silicon oxygen, m and n of The ratio (m/(m+n)) is preferably 0.25 or more and 1 or less.

本發明的透明複合體之特徵是使藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾的無機氧化物粒子以平均分散粒徑在1nm以上且20nm以下之方式分散於聚矽氧樹脂中而成者，同時，前述聚矽氧樹脂中含有矽氫化反應觸媒。 The transparent composite of the present invention is characterized in that the surface-modified inorganic oxide particles are bonded to each other by a polydimethyl methoxy siloxane backbone polymer having one functional group at one end, and the average dispersed particle diameter is 1 nm or more. The film is dispersed in a polyoxynoxy resin in a manner of not more than 20 nm, and the polyfluorene oxide resin contains a hydrazine hydrogenation reaction catalyst.

本發明的透明複合體之特徵是在將本發明的無機氧化物粒子與聚矽氧樹脂之複合組成物成形並固化為預定之形狀，或是在將前述複合組成物固化後予以成形而成者。 The transparent composite of the present invention is characterized in that the composite composition of the inorganic oxide particles of the present invention and the polyoxyxylene resin is formed into a predetermined shape or formed by curing the composite composition. .

本發明的無機氧化物粒子與聚矽氧樹脂之複合組成物的製造方法，其特徵是含有下述步驟：將無機氧化物粒子之表面以單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物來修飾，得到經表面修飾的平均分散粒徑為1nm以 上且20nm以下之無機氧化物粒子的步驟；以及將前述經表面修飾的平均分散粒徑為1nm以上且20nm以下之無機氧化物粒子、聚矽氧樹脂與反應觸媒混合的混合步驟。 A method for producing a composite composition of an inorganic oxide particle and a polyoxyxylene resin according to the present invention, which comprises the step of: polymerizing the surface of the inorganic oxide particle with a polyfunctional fluorene having one functional group at one end The oxane backbone polymer is modified to obtain a surface-modified average dispersed particle size of 1 nm. And a step of mixing the inorganic oxide particles having a surface-modified average dispersed particle diameter of 1 nm or more and 20 nm or less, and a polyfluorene oxide resin and a reaction catalyst.

本發明的無機氧化物粒子與聚矽氧樹脂之複合組成物，至少含有無機氧化物粒子、聚矽氧樹脂與反應觸媒；其中，該無機氧化物粒子是藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾，同時平均分散粒徑為1nm以上且20nm以下之無機氧化物粒子；聚矽氧樹脂含有乙烯基改質聚矽氧及氫改質聚矽氧；反應觸媒含有矽氫化反應觸媒。藉此，可大幅提升聚矽氧樹脂中之無機氧化物粒子之分散性。 The composite composition of the inorganic oxide particles and the polyfluorene oxide resin of the present invention contains at least inorganic oxide particles, a polyfluorene oxide resin and a reaction catalyst; wherein the inorganic oxide particles have one by one end of the bonded one-sided end Functionally modified polydimethyl methoxy siloxane backbone polymer and surface-modified, while uniformly dispersing inorganic oxide particles having a particle diameter of 1 nm or more and 20 nm or less; polyoxyn epoxide resin containing vinyl modified poly argon and hydrogen The polymerization catalyst contains a hydrogenation reaction catalyst. Thereby, the dispersibility of the inorganic oxide particles in the polyoxynoxy resin can be greatly improved.

因此，若使用此複合組成物，則在將無機氧化物粒子與聚矽氧樹脂複合時，可使分散性高，並且可防止硬化時的相分離/白化，故可得到維持透明性、耐熱性及耐光性且控制折射率之透明複合體。 Therefore, when the composite composition is used, when the inorganic oxide particles are combined with the polyoxynoxy resin, the dispersibility is high, and phase separation/whitening during curing can be prevented, so that transparency and heat resistance can be maintained. And a transparent composite that is light resistant and controls the refractive index.

依據本發明的透明複合體，使藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾的無機氧化物粒子，以平均分散粒徑為1nm以上且20nm以下之方式分散於聚矽氧樹脂中，同時，在前述聚矽氧樹脂中含有矽氫化反應觸媒。藉此，可容易地得到維持透明性、耐熱性及耐光性且抑制折射率之無機氧化物粒子與聚矽氧樹脂的透明複合體。 According to the transparent composite of the present invention, the surface-modified inorganic oxide particles are bonded by a polydimethyl methoxy siloxane backbone polymer having one functional group at one end, and the average dispersed particle diameter is 1 nm or more. The polyfluorene resin is dispersed in a manner of not more than 20 nm, and a rhodium hydrogenation reaction catalyst is contained in the polyfluorene oxide resin. Thereby, a transparent composite of the inorganic oxide particles and the polyoxynoxy resin which maintain the transparency, heat resistance, and light resistance and suppress the refractive index can be easily obtained.

依據本發明的透明複合體，係在將本發明的無機氧化 物粒子與聚矽氧樹脂的複合組合物成形並固化為預定之形狀，或是在將複合組合物固化後予以成形而成者。藉此，可容易得到維持透明性、耐熱性及耐光性且抑制折射率之無機氧化物粒子與聚矽氧樹脂的透明複合體。 The transparent composite according to the present invention is based on the inorganic oxidation of the present invention The composite composition of the particles and the polyoxyxylene resin is formed into a predetermined shape or formed by curing the composite composition. Thereby, a transparent composite of the inorganic oxide particles and the polyoxynoxy resin which maintain the transparency, the heat resistance, and the light resistance and which suppress the refractive index can be easily obtained.

本發明係有關無機氧化物粒子與聚矽氧樹脂之複合組成物及透明複合體。更詳細而言，係有關適合作為聚矽氧樹脂的填充劑材料使用，且可提升折射率、機械特性及氣體阻隔性並同時維持透明性的無機氧化物粒子，在分散於聚矽氧樹脂中時之分散性；及可防止硬化時的相分離/白化之無機氧化物粒子與聚矽氧樹脂的複合組成物；以及將此複合組成物予以成形固化而成的透明複合體。 The present invention relates to a composite composition of an inorganic oxide particle and a polyoxyxylene resin, and a transparent composite. More specifically, it is an inorganic oxide particle which is suitable for use as a filler material of a polyoxyxene resin and which can improve refractive index, mechanical properties, and gas barrier properties while maintaining transparency, and is dispersed in a polyoxyl resin. Dispersibility at the time; and a composite composition of inorganic oxide particles and polyoxynoxy resin which can prevent phase separation/whitening during hardening; and a transparent composite obtained by molding and curing the composite composition.

針對用以實施本發明之無機氧化物粒子與聚矽氧樹脂之複合組成物及透明複合體的理想形態，而進行說明。 A preferred embodiment of the composite composition of the inorganic oxide particles and the polyoxyxylene resin and the transparent composite for carrying out the present invention will be described.

此形態係為良好地理解發明主旨而具體說明者，並無特別限制，並非限定本發明者。在不脫離本發明主要意旨的範圍內，可做結構的加成、省略、替換及其他之變更。 This embodiment is specifically described for the purpose of well understanding the invention, and is not particularly limited, and is not intended to limit the invention. Additions, omissions, substitutions, and other modifications of the structure may be made without departing from the spirit and scope of the invention.

[無機氧化物粒子與聚矽氧樹脂的複合組成物] [Composite composition of inorganic oxide particles and polyfluorene oxide resin]

本實施形態的無機氧化物粒子與聚矽氧樹脂的複合組成物(以下也僅稱為「複合組成物」)，係將無機氧化物粒子分散到聚矽氧樹脂中所成的複合組成物，且為至少含有無機氧化物粒子、聚矽氧樹脂與反應觸媒的複合組成物；其中，無機氧化物粒子是藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾，同時平均 分散粒徑為1nm以上且20nm以下之無機氧化物粒子。 The composite composition of the inorganic oxide particles and the polyfluorene oxide resin of the present embodiment (hereinafter also referred to simply as "composite composition") is a composite composition obtained by dispersing inorganic oxide particles in a polyfluorene oxide resin. And a composite composition comprising at least inorganic oxide particles, a polyoxyxylene resin and a reaction catalyst; wherein the inorganic oxide particles are polymerized by combining dimethyl methoxy oxane having a functional group at one end Surface modification and average The inorganic oxide particles having a dispersed particle diameter of 1 nm or more and 20 nm or less are dispersed.

在此，「複合組成物」是不具有特定的形狀，而具有若一旦暫時變形則不會回復原來形狀的不可逆的變形性，其為後述之透明複合體的原料。 Here, the "composite composition" is an irreversible deformability which does not return to the original shape when it is temporarily deformed, and is a raw material of a transparent composite to be described later.

該複合組成物的狀態，係為例如顯示液狀或具有觸變性的凝膠狀態者。 The state of the composite composition is, for example, a liquid state showing a liquid state or a thixotropic property.

屬於無機氧化物粒子之成分的無機氧化物，並無特別限定，可列舉：矽(Si)等非金屬元素的氧化物；鋯(Zr)、鈦(Ti)、鋁(Al)、鐵(Fe)、銅(Cu)、鋅(Zn)、釔(Y)、鈮(Nb)、鉬(Mo)、銦(In)、錫(Sn)、鉭(Ta)、鎢(W)、鉛(Pb)、鉍(Bi)、鈰(Ce)、銻(Sb)、鍺(Ge)等金屬元素的氧化物。 The inorganic oxide which is a component of the inorganic oxide particles is not particularly limited, and examples thereof include an oxide of a non-metal element such as cerium (Si); zirconium (Zr), titanium (Ti), aluminum (Al), and iron (Fe). ), copper (Cu), zinc (Zn), yttrium (Y), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), tantalum (Ta), tungsten (W), lead (Pb) An oxide of a metal element such as bismuth (Bi), cerium (Ce), strontium (Sb) or germanium (Ge).

如此的無機氧化物，例如可列舉：氧化鋯(ZrO2)、氧化鈦(TiO2)、氧化矽(SiO2)、氧化鋁(Al2O3)、氧化鐵(Fe2O3、FeO、Fe3O4)、氧化銅(CuO、Cu2O)、氧化鋅(ZnO)、氧化釔(Y2O3)、氧化鈮(Nb2O5)、氧化鉬(MoO3)、氧化銦(In2O3、In2O)、氧化錫(SnO2)、氧化鉭(Ta2O5)、氧化鎢(WO3、W2O5)、氧化鉛(PbO、PbO2)、氧化鉍(Bi2O3)、氧化鈰(CeO2、Ce2O3)、氧化銻(Sb2O3、Sb2O5)、氧化鍺(GeO2、GeO)等。 Examples of such inorganic oxides include zirconium oxide (ZrO 2 ), titanium oxide (TiO 2 ), cerium oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), and iron oxide (Fe 2 O 3 , FeO, Fe 3 O 4 ), copper oxide (CuO, Cu 2 O), zinc oxide (ZnO), yttrium oxide (Y 2 O 3 ), niobium oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), indium oxide ( In 2 O 3 , In 2 O), tin oxide (SnO 2 ), tantalum oxide (Ta 2 O 5 ), tungsten oxide (WO 3 , W 2 O 5 ), lead oxide (PbO, PbO 2 ), yttrium oxide ( Bi 2 O 3 ), cerium oxide (CeO 2 , Ce 2 O 3 ), cerium oxide (Sb 2 O 3 , Sb 2 O 5 ), cerium oxide (GeO 2 , GeO), or the like.

在如此之無機氧化物中，也包含經添加錫之氧化銦(ITO：Indium Tin Oxide)、經氧化釔安定化之氧化鋯(YSZ：Yttria Stabilized Zirconia)等複合氧化物。 In such an inorganic oxide, a composite oxide such as tin oxide-doped indium tin oxide (ITO: Indium Tin Oxide) or yttria-stabilized zirconia (YSZ: Yttria Stabilized Zirconia) is also contained.

如此之無機氧化物，可單獨只使用1種，也可混合2種以上而使用。 The inorganic oxide may be used singly or in combination of two or more.

尤其，在將與聚矽氧樹脂的複合組成物予以高折射率 化時，係以具有高折射率，對可見光線為無色透明，並且硬度也高的氧化鋯(ZrO2)或氧化鈦(TiO2)為合適。 In particular, when the composite composition with the polyoxynene resin is made to have a high refractive index, it is a zirconia (ZrO 2 ) or titanium oxide (TiO) having a high refractive index, being colorless and transparent to visible light, and having high hardness. 2 ) is appropriate.

又，在將與聚矽氧樹脂的複合組成物予以低折射率化時，係以使用例如中空二氧化矽粒子或多孔質二氧化矽粒子等在粒子內具有空隙而使粒子整體成為低折射率之無機氧化物粒子為佳。 In addition, when the composite composition of the polyoxynene resin is reduced in refractive index, the particles are made to have a low refractive index by using voids in the particles, for example, using hollow cerium oxide particles or porous cerium oxide particles. The inorganic oxide particles are preferred.

在此無機氧化物粒子的複合組成物中之平均分散粒徑係以1nm以上且20nm以下為佳。平均分散粒徑是以3nm以上且10nm以下為更佳。 The average dispersed particle diameter of the composite composition of the inorganic oxide particles is preferably 1 nm or more and 20 nm or less. The average dispersed particle diameter is more preferably 3 nm or more and 10 nm or less.

在此，將無機氧化物粒子的平均分散粒徑限定在1nm以上且20nm以下的理由是如以下所述。平均分散粒徑未逹1nm時，構成此粒子的粒子一次粒徑也未逹1nm，而變得極小。因此，缺乏無機氧化物粒子的結晶性，而難以呈現折射率等粒子特性。另一方面，平均分散粒徑超過20nm時，由於無機氧化物粒子的瑞利散射(Rayleigh scattering)之影響會變大，故複合組成物的透明性會下降，或是將此複合組成物成形/固化所得到之透明複合體的透明性會下降。 Here, the reason why the average dispersed particle diameter of the inorganic oxide particles is limited to 1 nm or more and 20 nm or less is as follows. When the average dispersed particle diameter is less than 1 nm, the primary particle diameter of the particles constituting the particles is not less than 1 nm, and is extremely small. Therefore, the crystallinity of the inorganic oxide particles is lacking, and it is difficult to exhibit particle characteristics such as a refractive index. On the other hand, when the average dispersed particle diameter exceeds 20 nm, the influence of Rayleigh scattering of the inorganic oxide particles becomes large, so that the transparency of the composite composition is lowered, or the composite composition is formed/ The transparency of the transparent composite obtained by curing is lowered.

如此，由於無機氧化物粒子是奈米級尺寸的粒子，故在將此無機氧化物粒子分散於聚矽氧樹脂中而成的複合組成物、或是在將此複合組成物成形/固化所成之透明複合體中，光散射為小，可維持複合組成物或透明複合體的透明性。 As described above, since the inorganic oxide particles are particles having a nanometer size, the composite composition obtained by dispersing the inorganic oxide particles in the polyfluorene oxide resin or forming/curing the composite composition is formed. In the transparent composite, light scattering is small, and the transparency of the composite composition or the transparent composite can be maintained.

此無機氧化物粒子在複合組成物中之含有率，係以1 質量%以上且90質量%以下為佳，較佳是5質量%以上且90質量%以下，更佳是10質量%以上且85質量%以下。 The content of the inorganic oxide particles in the composite composition is 1 The mass% or more and 90% by mass or less are preferable, preferably 5% by mass or more and 90% by mass or less, and more preferably 10% by mass or more and 85% by mass or less.

在此，將無機氧化物粒子之含有率限定在1質量%以上且90質量%以下的理由是如以下所述。含有率未逹1質量%時，無機氧化物粒子之量會太少，在將無機氧化物粒子與聚矽氧樹脂複合時，難以呈現聚矽氧樹脂的光學特性或機械特性之變化，結果無法得到將無機氧化物粒子複合的效果，故而不佳。另一方面，含有率超過90質量%時，由於不能充分確保無機氧化物粒子之分散性，或在複合組成物中之流動性會下降而使成形性變差，故而不佳。 Here, the reason why the content ratio of the inorganic oxide particles is limited to 1% by mass or more and 90% by mass or less is as follows. When the content is less than 1% by mass, the amount of the inorganic oxide particles is too small. When the inorganic oxide particles are combined with the polyoxynoxy resin, it is difficult to exhibit changes in the optical properties or mechanical properties of the polyoxyxene resin. The effect of recombining the inorganic oxide particles is obtained, which is not preferable. On the other hand, when the content is more than 90% by mass, the dispersibility of the inorganic oxide particles is not sufficiently ensured, or the fluidity in the composite composition is lowered to deteriorate the moldability, which is not preferable.

其次，針對此無機氧化物粒子之表面修飾進行說明。 Next, the surface modification of this inorganic oxide particle will be described.

此無機氧化物粒子之表面，係以由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑來修飾。 The surface of the inorganic oxide particles is modified by a surface modifying agent composed of a polydimethyl methoxy siloxane backbone polymer having one functional group at one end.

此表面修飾劑具有聚二甲基矽氧烷骨幹、尤其是在主鏈具有直鏈狀的聚二甲基矽氧烷骨幹，並且在該主鏈的單邊末端(一端側)只具有1個屬於官能基之極性基。因此，當該官能基(極性基)選擇性地結合於無機氧化物粒子之表面時，另一側，亦即矽氧烷骨幹部分則變成朝向粒子外側(遠離無機氧化物粒子表面之方向)之形狀。 The surface modifier has a polydimethyl siloxane backbone, especially a polydimethyl siloxane backbone having a linear chain in the main chain, and has only one at one end (one end side) of the main chain. A polar group belonging to a functional group. Therefore, when the functional group (polar group) is selectively bonded to the surface of the inorganic oxide particle, the other side, that is, the backbone portion of the oxoxane, becomes toward the outside of the particle (in the direction away from the surface of the inorganic oxide particle). shape.

而且，由於此矽氧烷骨幹部分與聚矽氧樹脂的相溶性高，且親和性良好，故以由此聚二甲基矽氧烷骨幹聚合物所構成之表面修飾劑而經表面修飾的無機氧化物粒子，可均勻地分散於聚矽氧樹脂中，而可形成良好的複合組成物。 Moreover, since the backbone portion of the oxoxane has high compatibility with the polyoxyxene resin and good affinity, the surface-modified inorganic body is composed of the surface modifier composed of the polydimethyl methoxy siloxane backbone polymer. The oxide particles can be uniformly dispersed in the polyoxynoxy resin to form a good composite composition.

在此，「直鏈狀的聚二甲基矽氧烷骨幹」是表示在聚二甲基矽氧烷骨幹上不分枝(分歧)的意思。 Here, the "linear polydimethyl siloxane oxide backbone" means that it does not branch (divide) on the polydimethyl siloxane backbone.

在此，於該聚二甲基矽氧烷骨幹中有分枝(分歧)，或是屬於官能基之極性基位於矽氧烷骨幹的中間(官能基係與位於矽氧烷骨幹中間之矽結合)時，矽氧烷骨幹之至少一部分會容易朝向無機氧化物粒子之表面方向，或是朝向與粒子表面平行之方向。此時，朝向無機氧化物粒子之外側的矽氧烷骨幹量會減少，無機氧化物粒子與聚矽氧樹脂之間的相溶性或親和性有下降之虞。再者，在矽氧烷骨幹之方向上由於失去統一性，故發生矽氧烷骨幹彼此的纏繞或立體障礙，仍然有使無機氧化物粒子與聚矽氧樹脂之間的相溶性或親和性下降之虞。 Here, there is a branch (difference) in the backbone of the polydimethyl siloxane, or a polar group belonging to a functional group is located in the middle of the siloxane backbone (the functional group is combined with the ruthenium located in the middle of the siloxane backbone) At least a portion of the siloxane backbone may be oriented toward the surface of the inorganic oxide particles or in a direction parallel to the surface of the particles. At this time, the amount of the siloxane backbone to the outside of the inorganic oxide particles is reduced, and the compatibility or affinity between the inorganic oxide particles and the polyoxyxene resin is lowered. Furthermore, due to the loss of uniformity in the direction of the siloxane backbone, entanglement or steric hindrance of the siloxane backbone is caused, and the compatibility or affinity between the inorganic oxide particles and the polyoxyxene resin is still lowered. After that.

又，此表面修飾劑係只具有一個極性基的1個官能基者，並且，此官能基係因用於與無機氧化物粒子之結合中，故在與無機氧化物粒子結合之表面修飾劑中不存在有官能基。因此，不會有如在使用以往之多官能聚矽氧烷時，因未反應而殘留的官能基所造成的與聚矽氧樹脂之相溶性惡化，例如發生白濁化等之虞，可得到安定的複合組成物。 Further, the surface modifying agent is one functional group having only one polar group, and since the functional group is used for bonding with inorganic oxide particles, it is in a surface modifying agent combined with inorganic oxide particles. There are no functional groups. Therefore, when the conventional polyfunctional polyoxyalkylene is used, the compatibility with the polyoxyxylene resin due to the functional group remaining unreacted is deteriorated, for example, clouding or the like occurs, and stability can be obtained. Composite composition.

如此之表面修飾劑，係以具有單縮水甘油基醚末端聚二甲基矽氧烷及/或單羥基末端聚二甲基矽氧烷為佳。本發明中使用的單縮水甘油基醚末端聚二甲基矽氧烷之分子量是以500至10000為佳。又，本發明中使用的單羥基醚末端聚二甲基矽氧烷，分子量是以500至10000為佳。 Such a surface modifying agent is preferably a polyglycidyl ether terminal polydimethyl siloxane and/or a monohydroxy terminal polydimethyl siloxane. The molecular weight of the monoglycidyl ether terminal polydimethyl siloxane used in the present invention is preferably from 500 to 10,000. Further, the monohydroxy ether terminal polydimethyl siloxane used in the present invention preferably has a molecular weight of from 500 to 10,000.

此等表面修飾劑所具有之末端基中，單縮水甘油基醚 末端係藉由將屬於縮水甘油基之一部分的環氧基的部分進行開環而與無機氧化物粒子的表面的羥基結合，又，單羥基醚末端係藉由使末端的羥基與無機氧化物粒子的表面的羥基進行脫水縮合而結合。 Monoglycidyl ether in the terminal group of these surface modifiers The terminal end is bonded to the hydroxyl group on the surface of the inorganic oxide particle by ring-opening a portion of the epoxy group which is a part of the glycidyl group, and the terminal portion of the monohydroxy ether is caused by the terminal hydroxyl group and the inorganic oxide particle. The hydroxyl groups of the surface are combined by dehydration condensation.

此等表面修飾劑中，單縮水甘油基醚末端聚二甲基矽氧烷原本並不含有羥基，又，單羥基醚末端聚二甲基矽氧烷只有在與無機氧化物粒子結合之官能基中具有羥基。因此，在任一表面修飾劑中，在與無機氧化物粒子表面結合後，會不具有羥基、或是羥基存在於無機氧化物粒子之表面附近，而變成不妨礙與聚矽氧樹脂相溶的狀態。 Among these surface modifiers, the monoglycidyl ether terminal polydimethyl siloxane originally does not contain a hydroxyl group, and the monohydroxy ether terminal polydimethyl siloxane only has a functional group bonded to the inorganic oxide particles. Has a hydroxyl group. Therefore, in any of the surface modifiers, after bonding to the surface of the inorganic oxide particles, there is no hydroxyl group, or the hydroxyl group exists in the vicinity of the surface of the inorganic oxide particles, and does not interfere with the state of being compatible with the polyoxynoxide resin. .

又，以藉由此等表面修飾劑而經表面修飾的無機氧化物粒子與聚矽氧樹脂之複合組成物所得之透明性複合體，係收縮率小。藉此，不會發生透明複合體中之孔洞或碎裂，又，硬化之聚矽氧樹脂中的無機氧化物粒子之分散性亦保持為良好，而得到無缺陷的透明複合體。 Further, the transparent composite obtained by the composite composition of the surface-modified inorganic oxide particles and the polyoxyxylene resin by the surface modifier is small in shrinkage. Thereby, voids or chipping in the transparent composite do not occur, and the dispersibility of the inorganic oxide particles in the hardened polyoxyn resin is also kept good, and a defect-free transparent composite is obtained.

本實施形態的無機氧化物粒子，係以單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物來表面修飾，故對於聚矽氧樹脂，其相溶性或分散性優異。因此，聚矽氧樹脂本身並無特別之限制，只要是通常的聚矽氧樹脂，即可無問題地使用。 Since the inorganic oxide particles of the present embodiment are surface-modified with a polydimethyl methoxy siloxane backbone polymer having one functional group at one end, it is excellent in compatibility or dispersibility with the polyoxymethylene resin. Therefore, the polyoxymethylene resin itself is not particularly limited, and any conventional polyoxyxylene resin can be used without problems.

此等聚矽氧樹脂中，係以在室溫(25℃)以上且150℃左右以下會獲得硬化物的使用矽氫化反應之聚矽氧樹脂為特佳，如此之聚矽氧樹脂係以乙烯基改質聚矽氧及氫改質聚矽氧為適合。 Among these polyoxynoxy resins, a polyfluorene resin which is obtained by a hydrogenation reaction of a cured product at room temperature (25 ° C) or more and about 150 ° C or less is particularly preferable, and the polyoxyxylene resin is ethylene. The base modified polyfluorene and hydrogen modified polyoxyl is suitable.

乙烯基改質聚矽氧可列舉：兩末端乙烯基-二甲基聚矽氧、兩末端乙烯基二苯基-二甲基聚矽氧、兩末端乙烯基-苯基甲基聚矽氧、兩末端乙烯基-二乙基聚矽氧、側鏈乙烯基-二甲基聚矽氧、乙烯基甲基聚矽氧、乙烯基甲氧基聚矽氧、乙烯基樹脂分散物等。此等乙烯基改質聚矽氧可選擇1種來使用，也可組合2種以上而使用。 The vinyl modified polyfluorene oxide may be exemplified by a two-terminal vinyl-dimethyl polyfluorene oxide, a two-terminal vinyl diphenyl-dimethyl polyfluorene oxide, and a two-terminal vinyl-phenylmethyl polyoxyxene. Both ends are vinyl-diethylpolyfluorene, side chain vinyl-dimethylpolyoxyl, vinylmethylpolyoxyl, vinylmethoxypolyoxyl, vinyl resin dispersion, and the like. These vinyl modified polyfluorene oxides may be used alone or in combination of two or more.

氫改質聚矽氧可列舉：兩末端氫-二甲基聚矽氧、甲基氫-二甲基聚矽氧、甲基氫聚矽氧、乙基氫聚矽氧、甲基氫-苯基甲基聚矽氧、氫化物樹脂等，此等氫改質聚矽氧可選擇1種來使用，也可組合2種以上而使用。 Hydrogen-modified polyfluorene can be exemplified by hydrogen-dimethyl polyfluorene at both ends, methyl hydrogen-dimethyl polyfluorene oxide, methyl hydrogen polyoxynium oxide, ethyl hydrogen polyoxynium oxide, methyl hydrogen-benzene. Further, the hydrogen-modified polyfluorene oxide may be used alone or in combination of two or more.

此氫改質聚矽氧中，以含有下述式(1)所示之側鏈氫改質聚矽氧為佳： (惟，R1至R8是相互獨立的任意有機基(H除外)，m是1以上之整數，n是包含0的正整數)。 In the hydrogen-modified polyfluorene oxygen, it is preferred to contain a side chain hydrogen-modified polyfluorene oxygen represented by the following formula (1): (However, R 1 to R 8 are independently of each other any organic groups (except H), m is an integer of 1, n is a positive integer including 0).

在此，以側鏈氫改質聚矽氧烷為較佳之理由，係因在與乙烯基改質聚矽氧藉由矽氫化反應等而進行聚合硬化並形成聚矽氧樹脂聚合物時，與末端氫改質聚矽氧相比，其反應性為較高，更進一步，由於屬於反應基的氫改質聚矽氧的量可為較多，故交聯密度變高，結果可使得到之聚矽 氧樹脂聚合物的特性提高。 Here, the reason why the side chain hydrogen-modified polyoxyalkylene is preferable is that when the polymer is hardened by a hydrogenation reaction with a vinyl modified polyfluorene or the like, and a polyxanthene resin polymer is formed, Compared with the hydrogen-modified polyfluorene at the end, the reactivity is higher. Further, since the amount of hydrogen-modified polyfluorene which belongs to the reactive group can be more, the crosslinking density becomes higher, and as a result, the obtained polycondensation can be obtained.矽 The properties of the oxyresin polymer are improved.

又，在上述式(1)所示的側鏈氫改質聚矽氧中，m與n之比(m/(m+n))是以0.25以上且1以下為佳。比值(m/(m+n))是以0.30以上且0.70以下為較佳。 Further, in the side chain hydrogen-modified polyfluorene represented by the above formula (1), the ratio of m to n (m/(m+n)) is preferably 0.25 or more and 1 or less. The ratio (m/(m+n)) is preferably 0.30 or more and 0.70 or less.

在此，將m與n之比(m/(m+n))限定為0.25以上且1以下的理由是如下所述。首先，(m/(m+n))未逹0.25時，由於硬化時的交聯密度太少，故無機氧化物粒子的凝集/相分離速度會變得比聚矽氧樹脂之硬化速度更快，結果與聚矽氧樹脂硬化時會失去透明性。 Here, the reason why the ratio of m to n (m/(m+n)) is limited to 0.25 or more and 1 or less is as follows. First, when (m/(m+n)) is less than 0.25, since the crosslinking density at the time of hardening is too small, the aggregation/phase separation speed of the inorganic oxide particles becomes faster than the hardening speed of the polyoxymethylene resin. As a result, the polysiloxane resin loses transparency when it hardens.

其次，m與n之比(m/(m+n))雖以1為上限，但m與n之比(m/(m+n))愈大時，下述式(2)所示之含氫單元的含有率會變愈高： 在形成透明複合體後，與乙烯基改質聚矽氧未反應之單元比率也被認為會增加。但是，此未反應之含氫單元對於透明複合體之特性幾乎不會造成影響。所以，在側鏈氫改質聚矽氧中，m與n之比(m/(m+n))的最大值可為1。 Next, the ratio of m to n (m/(m+n)) is an upper limit of 1, but the larger the ratio of m to n (m/(m+n)), the one represented by the following formula (2) The content of hydrogen-containing units will become higher: The ratio of units unreacted with vinyl modified polyoxymethylene is also believed to increase after the formation of the transparent composite. However, this unreacted hydrogen-containing unit hardly affects the properties of the transparent composite. Therefore, in the side chain hydrogen-modified polyfluorene oxide, the ratio of m to n (m/(m+n)) may be a maximum of 1.

上述式(1)中，R1至R8是相互獨立的任意有機基(H除外)，其中之一部分或全部可相同。在此，「一部分相同」是指，不僅可為例如R1與R3與R4與R6為相同並且R1與R2與R5與R7與R8為互相不同般的只有一部分為同一種之情 形，亦可為例如R1與R3與R4為相同並且R2與R5與R7與R8為相同，而且R1與R2與R6為互相不同般的一部分互相為相同者的組合。 In the above formula (1), R 1 to R 8 are arbitrary organic groups (except H) which are independent of each other, and some or all of them may be the same. Here, "partially identical" means that not only R 1 and R 3 but R 4 and R 6 are the same, and R 1 and R 2 and R 5 and R 7 and R 8 are different from each other. In the same case, for example, R 1 and R 3 and R 4 are the same and R 2 and R 5 and R 7 and R 8 are the same, and R 1 and R 2 and R 6 are mutually different parts of each other. A combination of the same.

又，「有機基」是表示特性基、官能基、取代基等由有機物所構成的全部基，例如包含烷基、烷氧基等。 In addition, the "organic group" means all the groups composed of an organic substance such as a characteristic group, a functional group, and a substituent, and includes, for example, an alkyl group or an alkoxy group.

就此聚矽氧樹脂而言，關於其與無機氧化物粒子等混合後之複合組成物的特性，只要是不具有特定之形狀，而具有一旦變形即不會回復原來形狀的不可逆的變形性，並變成後述透明複合體的原料，例如為液狀或具有觸變性之凝膠狀之狀態者即可，其聚合度並無特別限定。 In the polyoxyxene resin, the properties of the composite composition which is mixed with the inorganic oxide particles or the like are irreversible deformability which does not return to the original shape upon deformation, as long as it does not have a specific shape. The raw material to be a transparent composite to be described later may be, for example, a liquid or a thixotropic gel, and the degree of polymerization is not particularly limited.

亦即，複合組成物只要為具有上述特性者，即可為單體、寡聚物(2至數百左右的聚合物)、聚合物(數百以上的聚合物)的任一者，亦可為組合此等而使聚合度具有廣範圍者。 In other words, the composite composition may be any of a monomer, an oligomer (a polymer of about 2 to several hundreds), and a polymer (a polymer of several hundreds or more) as long as it has the above characteristics. In order to combine these, the degree of polymerization has a wide range.

又，在此聚矽氧樹脂中，在不損及其特性之範圍內，也可添加抗氧化劑、離型劑、偶合劑、無機充填劑等。 Further, in the polyoxymethylene resin, an antioxidant, a release agent, a coupling agent, an inorganic filler, or the like may be added to the extent that the properties are not impaired.

本實施形態的複合組成物含有反應觸媒。 The composite composition of the present embodiment contains a reaction catalyst.

此反應觸媒係以含有矽氫化反應觸媒為佳。此矽氫化反應觸媒可列舉貴金屬系觸媒，並可適當選擇貴金屬的粉體、貴金屬鹽、貴金屬錯合物等。貴金屬系觸媒中是以鉑族系觸媒為佳，例如可列舉鉑系觸媒、銠系觸媒、鈀系觸媒等，尤其是以鉑系觸媒為佳。此鉑系觸媒可列舉：鉑微粉體、氯化鉑酸、鉑-烯烴錯合物、鉑-羰基錯合物等，此等可單獨或組合2種以上來使用。 The reaction catalyst is preferably a catalyst containing a hydrazine hydrogenation reaction. The catalyst for the hydrogenation reaction may be a noble metal catalyst, and a powder of a noble metal, a noble metal salt, a noble metal complex or the like may be appropriately selected. The noble metal-based catalyst is preferably a platinum-based catalyst, and examples thereof include a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst, and particularly a platinum-based catalyst. Examples of the platinum-based catalyst include a platinum fine powder, a platinum chloride acid, a platinum-olefin complex, and a platinum-carbonyl complex. These may be used alone or in combination of two or more.

又，本實施形態的複合組成物可含有有機溶劑。 Further, the composite composition of the present embodiment may contain an organic solvent.

在此，關於複合組成物含有有機溶劑之優點，提出下述論點。 Here, regarding the advantages of the composite composition containing an organic solvent, the following arguments are proposed.

第1優點，可列舉如控制複合組成物的黏度。例如，當無機氧化物粒子與聚矽氧樹脂的混合物為高黏度時，會有流動性惡化，發生後述之透明複合體的成形性下降或處理容易性下降之問題的情形，在此，為了解決消除此等問題，可藉由在混合物中添加有機溶劑，而使此混合物之黏度下降到所期望之黏度為止。無機氧化物粒子與聚矽氧樹脂的混合物的黏度是以在0.05Pa．s至10000Pa．s為佳，更佳是在0.1Pa．s至100Pa．s。 The first advantage is, for example, the control of the viscosity of the composite composition. For example, when the mixture of the inorganic oxide particles and the polyoxynene resin has a high viscosity, the fluidity is deteriorated, and the moldability of the transparent composite described later is lowered or the handling ease is lowered. Here, in order to solve the problem To eliminate these problems, the viscosity of the mixture can be lowered to the desired viscosity by adding an organic solvent to the mixture. The viscosity of the mixture of inorganic oxide particles and polyoxynoxide resin is at 0.05 Pa. s to 10000Pa. s is better, better at 0.1Pa. s to 100Pa. s.

第2優點，可列舉如容易混合/分散。例如，將經表面修飾劑所修飾的無機氧化物粒子，先分散於與所使用的聚矽氧樹脂為相溶性高的有機溶劑中而製成無機氧化物粒子分散液，並將此無機氧化物粒子分散液與聚矽氧樹脂混合/攪拌，因為無機氧化物粒子對於聚矽氧樹脂之分散性為非常高，故而為佳。 The second advantage is, for example, easy mixing/dispersion. For example, the inorganic oxide particles modified by the surface modifying agent are first dispersed in an organic solvent having high compatibility with the polyfluorene oxide resin used to form an inorganic oxide particle dispersion, and the inorganic oxide is added. The particle dispersion is mixed/stirred with the polyoxyxene resin, and it is preferred because the dispersion of the inorganic oxide particles to the polyoxymethylene resin is very high.

此有機溶劑係以使用疏水性溶劑為佳。其理由是因疏水性溶劑係適合作為使經表面修飾之無機氧化物的分散性高且與聚矽氧樹脂的相溶性高的溶劑。 This organic solvent is preferably a hydrophobic solvent. The reason for this is that the hydrophobic solvent is suitable as a solvent having high dispersibility of the surface-modified inorganic oxide and high compatibility with the polyfluorene oxide resin.

如此之疏水性溶劑係例如可適合使用：苯、甲苯、二甲苯、乙基苯等芳香族烴；二氯甲烷、氯仿、四氯化碳等含氯溶劑。此等溶劑中，可單獨使用1種或混合2種以上而使用。 Examples of such a hydrophobic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and chlorine-containing solvents such as dichloromethane, chloroform, and carbon tetrachloride. These solvents may be used alone or in combination of two or more.

此有機溶劑的含有率，只要是會得到上述等溶劑添加效果者即可，而無特別限定，但通常相對於經表面修飾之無機氧化物粒子與聚矽氧樹脂之合計量，係以400質量%以下為佳。有機溶劑的含有率較佳是在100質量%以下。其理由是若有機溶劑過剩存在，則在使用此複合組成物形成後述透明複合體時，會黏度過低而難以產生成形性，或是會需要花時間除去有機溶劑，因而不佳。 The content of the organic solvent is not particularly limited as long as the solvent-adding effect is obtained as described above, but is usually 400 mass in terms of the total amount of the surface-modified inorganic oxide particles and the polyoxyxylene resin. % below is better. The content of the organic solvent is preferably 100% by mass or less. The reason for this is that when the organic solvent is excessively present, when the composite composition described later is used to form a transparent composite described later, the viscosity is too low, and it is difficult to form moldability, or it takes time to remove the organic solvent, which is not preferable.

[複合組成物之製造方法] [Manufacturing method of composite composition]

本實施形態的複合組成物之製造方法為下述之方法：首先，將無機氧化物粒子的表面以單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物來修飾，形成經表面修飾的平均分散粒徑為1nm以上且20nm以下的無機氧化物粒子，其次，將此經表面修飾的平均分散粒徑為1nm以上且20nm以下的無機氧化物粒子、聚矽氧樹脂、與反應觸媒混合的方法。 The method for producing a composite composition according to the present embodiment is a method in which first, the surface of the inorganic oxide particles is modified by a polydimethyl methoxy siloxane backbone polymer having one functional group at one end. The inorganic oxide particles having a surface-modified average dispersed particle diameter of 1 nm or more and 20 nm or less, and the surface-modified average dispersed particle diameter of 1 nm or more and 20 nm or less of inorganic oxide particles, polyfluorene oxide resin, and reaction The method of catalyst mixing.

在此，將無機氧化物粒子的表面以單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物來修飾的方法，可列舉如下所示之方法。亦即，可列舉如下述之方法：首先，預先使特定之分散劑結合於無機氧化物粒子的表面，使其具有對於疏水性溶劑(有機溶劑)之分散性。其次，將此無機氧化物粒子分散於疏水性溶劑中，得到分散液。接著，在所得到之分散液中加入由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑，在此疏水性溶劑中，將預先結合於無機氧化物粒子之表面的特定分 散劑、與由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑進行置換。 Here, a method of modifying the surface of the inorganic oxide particles by a polydimethyl methoxy siloxane backbone polymer having one functional group at one end may be exemplified by the following method. That is, a method of first dispersing a specific dispersing agent on the surface of the inorganic oxide particles to have a dispersibility with respect to a hydrophobic solvent (organic solvent) can be mentioned. Next, this inorganic oxide particle was dispersed in a hydrophobic solvent to obtain a dispersion. Next, a surface modifier composed of a polydimethyl methoxy siloxane backbone polymer having one functional group at one end is added to the obtained dispersion, and in this hydrophobic solvent, it is previously bonded to inorganic oxidation. Specific fraction of the surface of the particle The powder is replaced with a surface modifying agent composed of a polydimethyl methoxy siloxane backbone polymer having one functional group at one end.

更詳細地說明上述方法。 The above method will be explained in more detail.

預先使特定之分散劑結合於無機氧化物粒子的表面，使其具有對於疏水性溶劑的分散性。 A specific dispersing agent is previously bonded to the surface of the inorganic oxide particles to have dispersibility with respect to the hydrophobic solvent.

結合有此特定分散劑的無機氧化物粒子係容易分散於疏水性溶劑中。又，結合有此特定分散劑之無機氧化物粒子，在與由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑為共存時，在前述無機氧化物粒子之表面中，可容易使已結合之特定分散劑與前述表面修飾劑發生置換。 The inorganic oxide particles incorporating such a specific dispersing agent are easily dispersed in a hydrophobic solvent. Further, the inorganic oxide particles incorporating the specific dispersing agent are present in the above-mentioned inorganic oxidation when a surface modifying agent composed of a polydimethyl methoxy siloxane backbone polymer having one functional group at one end is coexistent. In the surface of the particles, the specific dispersant to be combined can be easily replaced with the surface modifying agent.

特定之分散劑可列舉有機酸化合物或有機鹼化合物。有機酸化合物可列舉羧酸、磷酸、磺酸等，有機鹼化合物可列舉胺、磷腈鹼(phosphazene base)等。 Specific examples of the dispersant include organic acid compounds or organic base compounds. Examples of the organic acid compound include a carboxylic acid, a phosphoric acid, and a sulfonic acid. Examples of the organic base compound include an amine, a phosphazene base, and the like.

在此等分散劑中，以羧酸或胺為適用，其原因為該等可發揮作為使無機氧化物粒子分散之分散劑的機能，並且與表面修飾劑反應時可良好地脫離。 Among these dispersants, a carboxylic acid or an amine is suitable because the function as a dispersing agent for dispersing inorganic oxide particles can be exhibited, and it can be favorably removed when reacting with a surface modifying agent.

就羧酸而言，只要選擇使用從甲酸、醋酸、酪酸、戊酸、己酸、庚酸、辛酸、癸酸、月桂酸、硬脂酸等飽和脂肪酸、油酸等不飽和脂肪酸中選出之1種或2種以上即可。又，就胺而言，例如只要選擇使用從吡啶、聯吡啶等芳香族胺、三乙基胺、二乙基胺、單乙基胺、丁基胺等脂肪族胺中選出之1種或2種以上即可。 In the case of carboxylic acid, one selected from unsaturated fatty acids such as formic acid, acetic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, stearic acid, and the like, and unsaturated fatty acids such as oleic acid. Kind or more than two kinds. Further, as the amine, for example, one or two selected from the group consisting of an aromatic amine such as pyridine or bipyridine, an aliphatic amine such as triethylamine, diethylamine, monoethylamine or butylamine may be used. More than one species.

其次，使在表面結合有特定分散劑的無機氧化物粒子 分散於疏水性溶劑中。 Secondly, the inorganic oxide particles having a specific dispersant bonded to the surface Dispersed in a hydrophobic solvent.

就疏水性溶劑而言，只要是使前述表面結合有特定分散劑的無機氧化物粒子可安定分散者即可，但適合使用例如苯、甲苯、二甲苯、乙基苯等芳香族烴、二氯甲烷、氯仿、四氯化碳等含氯溶劑，此等溶劑中可使用1種或2種以上。 In the case of the hydrophobic solvent, the inorganic oxide particles having the specific dispersing agent bonded to the surface may be stably dispersed, but an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene, or dichlorobenzene is preferably used. A chlorine-containing solvent such as methane, chloroform or carbon tetrachloride may be used alone or in combination of two or more.

其次，在使前述表面結合有特定分散劑的無機氧化物粒子分散而成的疏水性溶劑中，加入前述之由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑，將此表面修飾劑與已結合在無機氧化物表面之特定分散劑進行置換。藉此，將無機氧化物粒子之表面，以由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑來修飾。 Next, in the hydrophobic solvent obtained by dispersing the inorganic oxide particles having the specific dispersing agent on the surface, the above-mentioned polydimethyl methoxy siloxane backbone polymer having one functional group at the unilateral terminal is added. a surface modifying agent that replaces the surface modifying agent with a particular dispersing agent that has been bound to the surface of the inorganic oxide. Thereby, the surface of the inorganic oxide particles is modified with a surface modifying agent composed of a polydimethyloxoxane backbone polymer having one functional group at one end.

此由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑的相對於無機氧化物粒子之質量比，相對於無機氧化物粒子之全質量，是以在5質量%以上且200質量%以下為佳，較佳是10質量%以上並且100質量%以下，更佳是20質量%以上並且100質量%以下。 The mass ratio of the surface modifier composed of the polydimethyl methoxy siloxane backbone polymer having one functional group at the unilateral end to the inorganic oxide particles is relative to the total mass of the inorganic oxide particles. It is preferably 5% by mass or more and 200% by mass or less, preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less.

在此，將表面修飾劑之質量比限定為5質量%以上且200質量%以下之理由，係因表面修飾劑之質量比未逹5質量%時，表面修飾劑之量太少而不能充分修飾無機氧化物粒子之表面，因此，此表面修飾不充分的無機氧化物粒子則難以與聚矽氧樹脂相溶，在與聚矽氧樹脂複合時會失去透明性。另一方面，表面修飾劑之質量比超過200質量%時， 在複合組成物中之表面修飾劑之比率會增大到無法無視之程度，因此，會大幅影響到複合組成物的特性，而有引起特性下降之虞。 Here, the reason why the mass ratio of the surface modifier is limited to 5% by mass or more and 200% by mass or less is that the amount of the surface modifying agent is too small to be sufficiently modified because the mass ratio of the surface modifying agent is less than 5% by mass. Since the surface of the inorganic oxide particles is such that the inorganic oxide particles having insufficient surface modification are difficult to be compatible with the polyoxynoxide resin, the transparency is lost when compounded with the polyoxynoxy resin. On the other hand, when the mass ratio of the surface modifier exceeds 200% by mass, The ratio of the surface modifier in the composite composition is increased to such an extent that it cannot be ignored, and therefore, the characteristics of the composite composition are greatly affected, and the characteristic is lowered.

如此，使用由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑，將此表面修飾劑在疏水性溶劑中與無機氧化物粒子反應，而使表面修飾劑之官能基(極性基)選擇性地對無機氧化物粒子配向/結合，另一方面，另一端側則在疏水性溶劑中分散，而成為朝向無機氧化物粒子之外側的形狀。因此，此等表面處理劑，係使官能基部分與無機氧化物粒子結合，另一端側則相對於無機氧化物粒子而成為呈放射狀遠離之形狀。 Thus, using a surface modifying agent composed of a polydimethyl methoxy siloxane backbone polymer having a functional group at one end, the surface modifying agent is reacted with the inorganic oxide particles in a hydrophobic solvent to form a surface. The functional group (polar group) of the modifier selectively aligns/bonds the inorganic oxide particles, while the other end side is dispersed in a hydrophobic solvent to have a shape toward the outside of the inorganic oxide particles. Therefore, these surface treatment agents combine the functional group portion with the inorganic oxide particles, and the other end side has a shape that is radially distant from the inorganic oxide particles.

由以上所述，可得到表面藉由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所修飾，同時平均分散粒徑為1nm以上且20nm以下的無機氧化物粒子。 From the above, inorganic oxide particles having a surface-modified polydimethylsiloxane oxide backbone polymer having one functional group at one end and having an average dispersed particle diameter of 1 nm or more and 20 nm or less can be obtained.

其次，將此經表面修飾的平均分散粒徑為1nm以上且20nm以下的無機氧化物粒子、聚矽氧樹脂與反應觸媒混合。此時，因應需要也可添加有機溶劑。 Next, the surface-modified inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less and a polyfluorene oxide resin are mixed with a reaction catalyst. At this time, an organic solvent may be added as needed.

在此，聚矽氧樹脂本身並無特別的限定，只要是藉由上述矽氫化反應而可硬化的乙烯基改質聚矽氧及氫改質聚矽氧之組合即可，而可毫無問題地使用。 Here, the polyoxymethylene resin itself is not particularly limited as long as it is a combination of a vinyl-modified polyfluorene oxygen which can be hardened by the above-mentioned hydrogenation reaction and a hydrogen-modified polyfluorene oxygen, and there is no problem. Use.

亦即，就乙烯基改質聚矽氧而言，可從兩末端乙烯基-二甲基聚矽氧、兩末端乙烯基二苯基-二甲基聚矽氧、兩末端乙烯基-苯基甲基聚矽氧、兩末端乙烯基-二乙基聚矽氧、側鏈乙烯基-二甲基聚矽氧、乙烯基甲基聚矽氧、乙烯 基甲氧基聚矽氧、乙烯基樹脂分散物等中選擇使用單獨1種或組合2種以上。 That is, in the case of vinyl-modified polyfluorene, it can be obtained from both ends of vinyl-dimethylpolyoxyl, two-terminal vinyldiphenyl-dimethylpolyoxyl, and both terminal vinyl-phenyl groups. Methyl polyfluorene, two-terminal vinyl-diethyl polyfluorene, side chain vinyl-dimethyl polyoxyl, vinyl methyl polyoxyl, ethylene One type or a combination of two or more types selected from the group consisting of a methoxy methoxypolyoxy group and a vinyl resin dispersion.

又，就氫改質聚矽氧而言，可從兩末端氫-二甲基聚矽氧、甲基氫-二甲基聚矽氧、甲基氫聚矽氧、乙基氫聚矽氧、甲基氫-苯基甲基聚矽氧、氫化物樹脂等中選擇使用單獨1種或是組合2種以上。 Further, in the case of hydrogen-modified polyfluorene, hydrogen-dimethyl polyoxane, methyl hydrogen-dimethyl polyoxyn, methyl hydrogen polyoxynium, ethyl hydrogen polyoxygen, One type of the methyl hydrogen-phenylmethyl polyfluorene oxide, a hydride resin, or the like may be used alone or in combination of two or more.

又，氫改質聚矽氧中，係以含有上述式(1)所示的側鏈氫改質聚矽氧為佳。 Further, in the hydrogen-modified polyfluorene oxygen, it is preferred to contain the side chain hydrogen-modified polyfluorene oxygen represented by the above formula (1).

在此，以側鏈氫改質聚矽氧為較佳之理由，係因在與乙烯基改質聚矽氧藉由矽氫化反應等而聚合硬化並形成聚矽氧樹脂聚合物時，與末端氫改質聚矽氧相比，其反應性為較高，更進一步，可使屬於反應基的氫改質聚矽氧的量變較多，故交聯密度變高，結果可使得到之聚矽氧樹脂聚合物的特性提高。 Here, the side chain hydrogen-modified polyfluorene is preferred because it is polymerized and hardened by a hydrogenation reaction with a vinyl group, and a polyanthracene resin polymer is formed by a hydrogenation reaction or the like. Compared with the modified polyfluorene oxygen, the reactivity is higher, and further, the amount of the hydrogen-modified polyfluorene which belongs to the reactive group is increased, so that the crosslinking density becomes high, and as a result, the obtained polyoxynoxy resin can be obtained. The properties of the polymer are improved.

再者，在上述式(2)所示的側鏈氫改質聚矽氧中，m與n之比(m/(m+n))是以0.25以上且1以下為佳。比值(m/(m+n))是以0.30以上且0.70以下為較佳。 Further, in the side chain hydrogen-modified polyfluorene represented by the above formula (2), the ratio of m to n (m/(m+n)) is preferably 0.25 or more and 1 or less. The ratio (m/(m+n)) is preferably 0.30 or more and 0.70 or less.

在此，將m與n之比(m/(m+n))限定為0.25以上的理由是如下所述。首先，m與n之比(m/(m+n))未逹0.25時，由於硬化時的交聯密度太少，故無機氧化物粒子的凝集/相分離速度也比聚矽氧樹脂之硬化速度更快，結果導致在與聚矽氧樹脂硬化時會失去透明性。 Here, the reason why the ratio of m to n (m/(m+n)) is limited to 0.25 or more is as follows. First, when the ratio of m to n (m/(m+n)) is less than 0.25, since the crosslinking density at the time of hardening is too small, the aggregation/phase separation speed of the inorganic oxide particles is also harder than that of the polyoxyl resin. The speed is faster, resulting in loss of transparency when hardened with the polyoxymethylene resin.

其次，m與n之比(m/(m+n))雖以1為上限，但m與n之比(m/(m+n))愈大時，上述式(2)所示之含氫單元的含有 率變愈高，在形成透明複合體後，與乙烯基改質聚矽氧未反應之單元比率也被認為會增加。但是，此未反應之含氫單元對於透明複合體之特性幾乎不會造成影響。因此，在側鏈氫改質聚矽氧中之m與n之比(m/(m+n))的最大值可為1。 Next, the ratio of m to n (m/(m+n)) is an upper limit of 1, but the larger the ratio of m to n (m/(m+n)), the one represented by the above formula (2) Hydrogen unit content The higher the rate, the higher the ratio of units unreacted with the vinyl modified polyoxyl group after the formation of the transparent composite is also considered to increase. However, this unreacted hydrogen-containing unit hardly affects the properties of the transparent composite. Therefore, the maximum ratio of m to n (m/(m+n)) in the side chain hydrogen-modified polyfluorene oxide may be 1.

將經表面修飾之無機氧化物粒子與聚矽氧樹脂混合的方法，並無特別限定，可使用混合機(mixer)、各種研磨機(mill)、外加超音波等以往已知的方法。 The method of mixing the surface-modified inorganic oxide particles and the polyoxynoxy resin is not particularly limited, and a conventionally known method such as a mixer, various mills, or ultrasonic waves can be used.

在此，藉由表面修飾劑而經表面修飾之無機氧化物粒子，亦可直接以粒子狀態與聚矽氧樹脂混合。但是，為了提高此經表面修飾之無機氧化物粒子的在聚矽氧樹脂中之分散性或混合容易性，較佳係先在對於使用此經表面修飾之無機氧化物粒子的聚矽氧樹脂為相溶性高的有機溶劑(疏水性溶劑)中進行再分散，然後將所得之無機氧化物粒子分散液與聚矽氧樹脂混合/攪拌。 Here, the surface-modified inorganic oxide particles by the surface modifying agent may be directly mixed with the polyoxyxylene resin in a particulate state. However, in order to improve the dispersibility or ease of mixing of the surface-modified inorganic oxide particles in the polyoxyxene resin, it is preferred to use a polyfluorene resin for the surface-modified inorganic oxide particles. The organic solvent (hydrophobic solvent) having high compatibility is redispersed, and then the obtained inorganic oxide particle dispersion is mixed/stirred with the polyoxyn resin.

亦即，將無機氧化物粒子直接投入至具有某種程度黏度的聚矽氧樹脂中並攪拌時，難以使此無機氧化物粒子在具有黏性的聚矽氧樹脂中以均勻且防止粒子凝集之方式分散，所得到之分散體中之無機氧化物粒子之分散性也差，再者，使無機氧化物粒子在具有黏性的聚矽氧樹脂中分散之步驟本身即需要花費很大的勞力。 That is, when the inorganic oxide particles are directly introduced into a polyfluorene resin having a certain viscosity and stirred, it is difficult to make the inorganic oxide particles uniform in the viscous polyoxyn resin and prevent the particles from aggregating. The dispersion of the method is also inferior in the dispersibility of the inorganic oxide particles in the obtained dispersion. Further, the step of dispersing the inorganic oxide particles in the viscous polyoxynoxy resin itself requires a lot of labor.

另一方面，將經表面修飾之無機氧化物粒子暫時再分散到對聚矽氧樹脂為相溶性高的有機溶劑中時，由於有機溶劑本身為低黏度，故無機氧化物粒子會均勻地分散於有 機溶劑中，而成為低黏度之無機氧化物粒子分散液。在此，只要將該均勻分散有無機氧化物粒子的分散液與聚矽氧樹脂混合，由於是液體彼此的混合，故即使聚矽氧樹脂為具有某種程度黏度者，也可與低黏度之分散液均勻地混合，結果，無機氧化物粒子會容易且均勻地分散於聚矽氧樹脂中。再者，低黏度之無機氧化物粒子分散液與具有低黏性之聚矽氧樹脂混合之步驟本身，由於是溶液彼此間的混合步驟，故不需要太多的勞力。 On the other hand, when the surface-modified inorganic oxide particles are temporarily redispersed into an organic solvent having high compatibility with the polyoxyxene resin, since the organic solvent itself has a low viscosity, the inorganic oxide particles are uniformly dispersed in the inorganic oxide particles. Have In the organic solvent, it becomes a low viscosity inorganic oxide particle dispersion. Here, if the dispersion liquid in which the inorganic oxide particles are uniformly dispersed is mixed with the polyoxynoxy resin, since the liquids are mixed with each other, even if the polyoxyxene resin has a certain viscosity, it can be used with a low viscosity. The dispersion is uniformly mixed, and as a result, the inorganic oxide particles are easily and uniformly dispersed in the polyoxynoxy resin. Further, the step of mixing the low-viscosity inorganic oxide particle dispersion with the low-viscosity polyoxynoxy resin itself does not require much labor because it is a mixing step between the solutions.

再者，經表面修飾之無機氧化物粒子與聚矽氧樹脂之混合物若為高黏度時，該混合物之流動性會惡化，而會有導致後述透明複合體的成形性下降或處理容易性下降的問題。 Further, when the mixture of the surface-modified inorganic oxide particles and the polyoxyxylene resin has a high viscosity, the fluidity of the mixture is deteriorated, and the formability of the transparent composite to be described later is lowered or the ease of handling is lowered. problem.

為了防止此等問題，在混合無機氧化物粒子與聚矽氧樹脂時，較佳係添加適當之溶劑，例如添加使經表面修飾之無機氧化物粒子的分散性高且與聚矽氧樹脂之相溶性也高之有機溶劑，先將所得混合物之黏度降低。 In order to prevent such problems, when mixing the inorganic oxide particles and the polyoxyxylene resin, it is preferred to add a suitable solvent, for example, to increase the dispersibility of the surface-modified inorganic oxide particles and the phase of the polyoxyxene resin. An organic solvent which is also highly soluble, first reduces the viscosity of the resulting mixture.

如此之有機溶劑係以使用疏水性溶劑為佳，例如，適合使用苯、甲苯、二甲苯、乙基苯等芳香族烴；二氯甲烷、氯仿、四氯化碳等含氯溶劑。此等溶劑中可單獨使用1種或混合2種以上而使用。 The organic solvent is preferably a hydrophobic solvent. For example, an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene; or a chlorine-containing solvent such as dichloromethane, chloroform or carbon tetrachloride is preferably used. These solvents may be used alone or in combination of two or more.

又，此有機溶劑的含有率，只要是會得到上述溶劑添加效果者即可，而無特別限定，但通常相對於經表面修飾之無機氧化物粒子與聚矽氧樹脂之合計量，是以400質量%以下為佳。有機溶劑的含有率是以在100質量%以下為較 佳。其理由是若有機溶劑過剩存在，則在使用此複合組成物形成後述透明複合體時，會因黏度過低而難以產生成形性，或是需要花時間除去有機溶劑，故而不佳。 In addition, the content of the organic solvent is not particularly limited as long as the effect of the solvent addition is obtained, but usually it is 400 in terms of the total amount of the surface-modified inorganic oxide particles and the polyoxyxylene resin. The mass % or less is preferred. The content of the organic solvent is 100% by mass or less. good. The reason for this is that when the organic compound is excessively formed, when the composite composition described later is used to form a transparent composite described later, it is difficult to form moldability because the viscosity is too low, or it takes a long time to remove the organic solvent, which is not preferable.

將經表面修飾之無機氧化物粒子與聚矽氧樹脂混合的具體方法，例如，可列舉：(1)使無機氧化物粒子再分散在有機溶劑中後，將聚矽氧樹脂投入該分散液中，混合攪拌的方法；(2)將無機氧化物粒子與聚矽氧樹脂混合後，在此混合物中添加適宜之有機溶劑，使用混合機等進行攪拌/混合而調整黏度，製成具有流動性之混合物的方法等。 Specific examples of the method of mixing the surface-modified inorganic oxide particles with the polyfluorene oxide resin include, for example, (1) after redispersing the inorganic oxide particles in an organic solvent, and then introducing the polyfluorene oxide resin into the dispersion. (2) mixing inorganic oxide particles with polyfluorene oxide resin, adding a suitable organic solvent to the mixture, and stirring/mixing using a mixer or the like to adjust the viscosity to obtain fluidity. The method of the mixture, etc.

當因添加有機溶劑而使所得之混合物之黏度變低時，也可藉由將有機溶劑的一部分或全部以揮發等除去，而進行黏度的調整(高黏度化)。 When the viscosity of the obtained mixture is lowered by the addition of an organic solvent, the viscosity can be adjusted (high viscosity) by removing a part or all of the organic solvent by volatilization or the like.

如上操作，可得到本實施形態的複合組成物。 As described above, the composite composition of the present embodiment can be obtained.

[透明複合體] [transparent complex]

本實施形態的透明複合體，係使藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾的無機氧化物粒子以平均分散粒徑為1nm以上且20nm以下之方式分散於聚矽氧樹脂中而成者，同時，在前述聚矽氧樹脂中含有矽氫化反應觸媒。在此透明複合體中，基本上不含有機溶劑，尤其是疏水性溶劑，即使含有也是極微量。 The transparent composite of the present embodiment has an average particle diameter of 1 nm or more by surface-modified inorganic oxide particles by combining a polydimethyl methoxy siloxane backbone polymer having one functional group at one end. The polyfluorene resin is dispersed in a manner of 20 nm or less, and the ruthenium hydrogenation reaction catalyst is contained in the polyfluorene oxide resin. In this transparent composite, it is substantially free of an organic solvent, especially a hydrophobic solvent, even if it is contained in a very small amount.

在此，「透明複合體」雖具有特定之形狀，但此「具有預定之形狀」是指，透明複合體不具有液狀、凝膠狀等之不可逆的變形性，而是配合使用的目的或方法而可維持一定的形狀之意思。亦即，包含通常幾乎不變形的固體狀， 此外亦包含橡膠狀等具有彈性變形性(形狀復原性)者，形狀本身並不顯示為特定之形狀。 Here, the "transparent composite" has a specific shape, but the "predetermined shape" means that the transparent composite does not have irreversible deformability such as liquid or gel, but is used for the purpose of use or The method can maintain a certain shape. That is, it contains a solid that is generally hardly deformed, In addition, it also includes elastic deformability (shape recovery property) such as rubber, and the shape itself is not shown as a specific shape.

此透明複合體，係藉由提高上述複合組成物中之聚矽氧樹脂之聚合度或交聯度、或是在聚矽氧樹脂與表面修飾劑的矽氧烷骨幹之間的聚合度或交聯度，而可得到具有預定形狀的狀態。因此，構成此透明複合體的各成分，亦即，關於以由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物所構成的表面修飾劑來修飾表面的無機氧化物粒子、聚矽氧樹脂、反應觸媒的3成分，係與上述複合組成物相同。 The transparent composite is obtained by increasing the degree of polymerization or crosslinking of the polyoxyxene resin in the composite composition, or the degree of polymerization or the degree of polymerization between the polyoxyxylene resin and the siloxane backbone of the surface modifier. With the degree of association, a state having a predetermined shape can be obtained. Therefore, the components constituting the transparent composite, that is, the surface-modifying agent composed of the polydimethyl methoxy siloxane backbone polymer having one functional group at the unilateral terminal, modify the surface of the inorganic oxide particles. The three components of the polyoxyxylene resin and the reaction catalyst are the same as those of the above composite composition.

在此透明複合體中，構成此透明複合體本身的經表面修飾之無機氧化物粒子之與聚矽氧樹脂之相溶性及親和性高，在聚矽氧樹脂中之分散性良好。因此，無機氧化物粒子與聚矽氧樹脂不會發生相分離，亦不會發生無機氧化物粒子之凝集等現象。因此，亦不會有因該等現象所導致之光學特性、機械特性、熱安定性等的劣化之虞，可維持良好的特性。 In the transparent composite, the surface-modified inorganic oxide particles constituting the transparent composite itself have high compatibility and affinity with the polyoxyxene resin, and have good dispersibility in the polyoxynoxy resin. Therefore, the inorganic oxide particles and the polyoxynized resin are not phase-separated, and aggregation of the inorganic oxide particles does not occur. Therefore, there is no deterioration in optical characteristics, mechanical properties, thermal stability, and the like due to such phenomena, and good characteristics can be maintained.

又，如上所述，使此聚矽氧樹脂藉由反應觸媒而硬化時，聚矽氧樹脂的硬化速度，係比無機氧化物粒子的凝集/相分離速度還快。因此，在所得到的透明複合體之中，無機氧化物粒子不會凝集，透明性也高。此外，屬於透明複合體之形成材料的複合組成物，係因為不使用螯合劑，故也不會有著色於透明複合體之虞。 Further, as described above, when the polyoxyxylene resin is cured by the reaction catalyst, the curing rate of the polyoxyxene resin is faster than the aggregation/phase separation rate of the inorganic oxide particles. Therefore, among the obtained transparent composites, the inorganic oxide particles do not aggregate and have high transparency. Further, since the composite composition which is a material for forming a transparent composite does not use a chelating agent, it does not have a coloration in the transparent composite.

又，在此透明複合體中含有的無機氧化物粒子之平均 分散粒徑係作成20nm以下。因此，可抑制若平均分散粒徑超過20nm則使影響變大的瑞利散射(Rayleigh scattering)之發生，透明複合體之透明性也不會下降。 Moreover, the average of the inorganic oxide particles contained in the transparent composite The dispersed particle size is made 20 nm or less. Therefore, it is possible to suppress the occurrence of Rayleigh scattering when the average dispersed particle diameter exceeds 20 nm, and the transparency of the transparent composite does not decrease.

如此，由於無機氧化物粒子是奈米級尺寸之粒子，故在將此無機氧化物粒子分散到聚矽氧樹脂中而成之複合組成物或是透明複合體中，光散射亦小，可維持複合組成物或透明複合體之透明性。 Thus, since the inorganic oxide particles are particles having a nanometer size, the light scattering is small and can be maintained in the composite composition or the transparent composite in which the inorganic oxide particles are dispersed in the polyoxynoxide resin. The transparency of the composite composition or transparent composite.

再者，在此透明複合體中含有的無機氧化物粒子之平均分散粒徑因為是設定為1nm以上，故此無機氧化物粒子的平均一次粒徑不會成為會使結晶性之維持變下降的未逹1nm的範圍。於是，此無機氧化物粒子可維持良好的結晶性。 In addition, since the average dispersed particle diameter of the inorganic oxide particles contained in the transparent composite is set to be 1 nm or more, the average primary particle diameter of the inorganic oxide particles does not become a decrease in the maintenance of crystallinity.逹 1nm range. Thus, the inorganic oxide particles can maintain good crystallinity.

如此，因為維持無機氧化物粒子的結晶性，故無機氧化物粒子本身所具有的特性，亦即，折射率或硬度、耐熱性等特性不會劣化。因此，將無機氧化物粒子與聚矽氧樹脂複合後所作成之透明複合體可得到充分的效果。 As described above, since the crystallinity of the inorganic oxide particles is maintained, the properties of the inorganic oxide particles themselves, that is, the properties such as refractive index, hardness, and heat resistance are not deteriorated. Therefore, a transparent composite obtained by combining inorganic oxide particles and a polyoxynoxy resin can obtain a sufficient effect.

在此，針對透明複合體的效果進行說明。 Here, the effect of the transparent composite will be described.

[光學的特性] [Optical characteristics]

透明複合體的光學特性可列舉折射率的控制。 The optical characteristics of the transparent composite can be exemplified by the control of the refractive index.

由於聚矽氧樹脂的折射率為1.4左右，故若將聚矽氧樹脂與折射率比該聚矽氧樹脂高的高折射率氧化物粒子進行複合，相較於聚矽氧樹脂單獨之情形，可將透明複合體的折射率更為提高。 Since the refractive index of the polyoxyxene resin is about 1.4, if the polyfluorene oxide resin is combined with the high refractive index oxide particles having a higher refractive index than the polyoxynoxy resin, compared to the case where the polyoxynoxy resin is used alone, The refractive index of the transparent composite can be further increased.

尤其與折射率為2以上的高折射率無機氧化物粒子， 例如與正方晶氧化鋯(折射率：2.15)或氧化鈦(折射率：2.6左右)複合係為有效，藉由使用此等高折射率無機氧化物粒子，可將透明複合體之折射率提高成比聚矽氧樹脂單獨之情形高0.1至0.2左右，亦即可提高到1.5至1.65左右為止。 In particular, high refractive index inorganic oxide particles having a refractive index of 2 or more, For example, it is effective to combine with tetragonal zirconia (refractive index: 2.15) or titanium oxide (refractive index: about 2.6), and by using such high refractive index inorganic oxide particles, the refractive index of the transparent composite can be increased to It is about 0.1 to 0.2 higher than that of the polyoxyl resin alone, and can be raised to about 1.5 to 1.65.

關於此透明複合體之透明性，如上所述，藉由將無機氧化物粒子之平均分散粒徑設定在20nm以下，可充分壓低光散射。因而，在該透明複合體中，可充分保持透明性。 As described above, by setting the average dispersed particle diameter of the inorganic oxide particles to 20 nm or less, the transparency of the transparent composite can sufficiently reduce the light scattering. Therefore, in the transparent composite, transparency can be sufficiently maintained.

又，藉由將如中空二氧化矽粒子或多孔質二氧化矽粒子般在粒子內有空隙而使粒子整體變成比聚矽氧樹脂更低折射率的無機氧化物粒子、與聚矽氧樹脂複合，則相較於聚矽氧樹脂單獨之情形，可使透明複合體之折射率更為下降。 Further, by having voids in the particles like hollow cerium oxide particles or porous cerium oxide particles, the particles as a whole become inorganic oxide particles having a lower refractive index than the polyoxyn oxyresin, and are compounded with polyoxyn oxyresin. Further, the refractive index of the transparent composite can be further lowered as compared with the case where the polyoxyxylene resin is used alone.

[機械特性] [Mechanical characteristics]

透明複合體的機械特性可列舉如：相較於樹脂單獨之情形，使硬度更為提高。 The mechanical properties of the transparent composite include, for example, a higher hardness than the case of the resin alone.

通常之無機氧化物粒子係相較於聚矽氧樹脂而為硬度較高，藉由將此無機氧化物粒子與聚矽氧樹脂複合，相較於聚矽氧樹脂單獨的情形，可將透明複合體的表面硬度更為提高。藉此，可使透明複合體的耐擦傷性提高，又，可提高透明複合體本身的尺寸精度。 Generally, the inorganic oxide particles are higher in hardness than the polyoxynoxy resin, and by combining the inorganic oxide particles with the polyoxynoxy resin, the transparent composite can be used as compared with the case of the polyoxynoxy resin alone. The surface hardness of the body is further improved. Thereby, the scratch resistance of the transparent composite can be improved, and the dimensional accuracy of the transparent composite itself can be improved.

尤其氧化鋯係在氧化物系陶瓷中也是屬於高硬度，故在藉由複合化所致之表面硬度提升方面可發揮高效果。 In particular, since zirconia is also high in hardness in the oxide-based ceramics, it has a high effect in terms of surface hardness improvement by compositing.

[熱安定性及化學安定性] [Thermal stability and chemical stability]

聚矽氧樹脂由於其本身在骨幹中含有矽(Si)，故與通常的樹脂相比，其耐熱性或耐藥品性等熱安定性及化學安定性優異。另一方面，無機氧化物粒子在耐熱性方面勝過聚矽氧樹脂。因此，若選定化學安定性高的無機氧化物粒子，並將此化學安定性高的無機氧化物粒子與聚矽氧樹脂複合，即可使所得之透明複合體的熱安定性或化學安定性相較於聚矽氧樹脂單獨之情形而更為提高。 Since the polysiloxane resin itself contains bismuth (Si) in the backbone, it is excellent in thermal stability and chemical stability such as heat resistance and chemical resistance as compared with a normal resin. On the other hand, the inorganic oxide particles outperform the polyoxyl resin in heat resistance. Therefore, if inorganic oxide particles having high chemical stability are selected and the inorganic oxide particles having high chemical stability are combined with polyoxynoxy resin, the thermal stability or chemical stability of the obtained transparent composite can be obtained. It is more improved than the case where the polyoxymethylene resin is used alone.

在此，已知聚矽氧樹脂是與疏水性溶劑的相溶性高，而為疏水性(撥水性)，但其富含柔軟性，對於水蒸氣之氣體阻隔性係較其他樹脂而為較低。 Here, it is known that a polyoxyxene resin has high compatibility with a hydrophobic solvent and is hydrophobic (water repellency), but it is rich in flexibility, and gas barrier properties against water vapor are lower than those of other resins. .

本實施形態的透明複合體中，氣體阻隔性優異之無機氧化物粒子係均勻地分散於透明複合體之內部，再者，因為無機氧化物粒子與聚矽氧樹脂之結合性高，故在透明複合體中之對於水蒸氣之氣體阻隔性，係相較於聚矽氧樹脂單獨之情形，而可改善成較高的狀態。 In the transparent composite of the present embodiment, the inorganic oxide particles having excellent gas barrier properties are uniformly dispersed in the transparent composite, and further, since the inorganic oxide particles and the polyoxyxylene resin have high binding properties, they are transparent. The gas barrier property to water vapor in the composite can be improved to a higher state than in the case of the polyoxyxylene resin alone.

此透明複合體可適合使用於光學透鏡用。其理由係因若依據此透明複合體，藉由將高折射率之無機氧化物粒子、尤其是將氧化鋯與聚矽氧樹脂複合，即可使所得之透明複合體的折射率，例如從聚矽氧樹脂單獨之情形時之1.4，提高至1.65左右。又，由於相較於聚矽氧樹脂單獨之情形而使硬度提高，故亦可謀求尺寸精度之提高。於是，可提高光學元件之設計自由度。 This transparent composite can be suitably used for an optical lens. The reason is that, according to the transparent composite, the refractive index of the obtained transparent composite can be made, for example, from agglomerated by combining high refractive index inorganic oxide particles, in particular, zirconia and polyoxynoxy resin. In the case of a silicone resin alone, 1.4 is increased to about 1.65. Further, since the hardness is improved as compared with the case where the polyoxymethylene resin is used alone, dimensional accuracy can be improved. Thus, the degree of freedom in designing the optical element can be improved.

結果，例如，相較於在光學透鏡中單獨使用聚矽氧樹脂之情形，而可進行小型化、薄型化、積體化、提高集光 效率、減少折射率波長之依頼性等。因此，可期待使用此種光學元件的機械之CCD或CMOS照相機等的特性提升，例如高解像度化或高感度化。 As a result, for example, it is possible to reduce the size, thickness, integration, and light collection as compared with the case where the polyoxynoxy resin is used alone in the optical lens. Efficiency, reduction of refractive index wavelength dependence, etc. Therefore, it is expected that the characteristics of a mechanical CCD or CMOS camera using such an optical element can be improved, for example, high resolution or high sensitivity.

又，此透明複合體可適合作為屬於發光元件的LED之密封材而使用。其理由係因此透明複合體相較於單獨的聚矽氧樹脂而為高折射率，故在作為屬於發光元件的LED之密封材而使用時，可提升與經密封材覆蓋之發光體或用以形成發光體之基板等折射率高之構件(屬於LED之發光體的半導體材料的折射率是2.5左右，將半導體材料製成膜之透明性基板的折射率是1.76左右)的折射率整合性。因此，在從LED之發光體射出發光到外部之過程中，可降低內部反射。 Further, the transparent composite can be suitably used as a sealing material for an LED belonging to a light-emitting element. The reason for this is that the transparent composite has a high refractive index as compared with the individual polyoxynoxy resin. Therefore, when used as a sealing material for an LED belonging to a light-emitting element, the light-emitting body covered with the sealed material can be used or used. A refractive index integration property of a member having a high refractive index such as a substrate on which an illuminant is formed (a refractive index of a semiconductor material belonging to an illuminant of an LED is about 2.5, and a refractive index of a transparent substrate in which a semiconductor material is a film is about 1.76). Therefore, internal reflection can be reduced in the process of emitting light from the illuminator of the LED to the outside.

亦即，藉由將本實施形態的透明複合體用於LED之密封材，即可將LED之取出光效率改善10%至15%左右，結果可提高LED之亮度。 In other words, by using the transparent composite of the present embodiment for the sealing material of the LED, the light extraction efficiency of the LED can be improved by about 10% to 15%, and as a result, the brightness of the LED can be improved.

再者，因為此透明複合體之對水蒸氣之氣體阻隔性高，故可抑制從外部滲入之水分，並可抑制發光區域之劣化。因此，可謀求發光元件之長壽命化。 Further, since the transparent composite has high gas barrier property against water vapor, moisture permeating from the outside can be suppressed, and deterioration of the light-emitting region can be suppressed. Therefore, it is possible to extend the life of the light-emitting element.

又，此透明複合體亦可適合作為有機EL元件之密封材而使用。其理由是在將此透明複合體作為有機EL元件之密封材而使用時，由於對水蒸氣之氣體阻隔性較高，故可抑制從外部滲入之水分，可抑制發光區域之劣化。又，透明複合體中之無機氧化物粒子可有效地抑制氧氣之穿透，故同樣地可抑制發光區域之劣化。因此，將本實施形態的透 明複合體作為有機EL元件之密封材使用時，可謀求有機EL元件中之發光元件的長壽命化。 Moreover, this transparent composite can also be suitably used as a sealing material of an organic electroluminescent element. The reason for this is that when the transparent composite is used as a sealing material for an organic EL device, since the gas barrier property against water vapor is high, moisture permeating from the outside can be suppressed, and deterioration of the light-emitting region can be suppressed. Further, since the inorganic oxide particles in the transparent composite can effectively suppress the penetration of oxygen, the deterioration of the light-emitting region can be suppressed similarly. Therefore, the penetration of this embodiment When the bright composite is used as a sealing material for an organic EL device, the life of the light-emitting device in the organic EL device can be extended.

[透明複合體的製造方法] [Method of Manufacturing Transparent Composite]

本實施形態的透明複合體係可藉由下述製程而得到：在將本實施形態的複合組成物成形並固化為預定之形狀，或是在將前述複合組成物固化後予以成形為預定之形狀。 The transparent composite system of the present embodiment can be obtained by molding and curing the composite composition of the present embodiment into a predetermined shape or by molding the composite composition into a predetermined shape.

本實施形態的製造方法中，「成形並固化為預定之形狀的方法」是如以下所述。 In the production method of the present embodiment, the "method of molding and solidifying into a predetermined shape" is as follows.

首先，將本實施形態的複合組成物使用模具或模框而形成，或是充填到模具或模框狀的容器中，藉此可得到成形為目的形狀的成形體或充填物。 First, the composite composition of the present embodiment is formed by using a mold or a mold, or is filled in a mold or a frame-shaped container, whereby a molded body or a filler formed into a desired shape can be obtained.

此時，使用之複合組成物的黏度高時，較佳係先添加有機溶劑等並加以攪拌/混合使黏度下降，而先調整成適合成形或充填的黏度。 In this case, when the viscosity of the composite composition to be used is high, it is preferred to add an organic solvent or the like first, and stir or mix to lower the viscosity, and first adjust the viscosity suitable for molding or filling.

另一方面，使用之複合組成物的黏度低時，較佳係先將聚矽氧樹脂彼此或聚矽氧樹脂與表面修飾劑之一部分以下述方式進行聚合或交聯，或是當複合組成物含有有機溶劑時，將此有機溶劑之一部分或全部藉由揮發等而除去以提高黏度，而先調整成適合成形或充填的黏度。 On the other hand, when the viscosity of the composite composition to be used is low, it is preferred to polymerize or crosslink the polyfluorene oxide resin or a part of the polyoxyxylene resin and the surface modifier in the following manner, or as a composite composition. When an organic solvent is contained, part or all of the organic solvent is removed by volatilization or the like to increase the viscosity, and is first adjusted to a viscosity suitable for forming or filling.

其次，將此成形體或充填物直接在室溫(25℃左右)中或是加溫至預定溫度(室溫至150℃，更佳是80℃至150℃)而靜置預定時間，對於此複合組成物中之聚矽氧樹脂或表面修飾劑經由反應觸媒而進行聚合或交聯等反應，以提高聚矽氧樹脂彼此或聚矽氧樹脂與表面修飾劑間之結合度 (聚合度)。 Next, the shaped body or the filling is allowed to stand at room temperature (about 25 ° C) or warmed to a predetermined temperature (room temperature to 150 ° C, more preferably 80 ° C to 150 ° C) and allowed to stand for a predetermined time. The polyoxyxylene resin or the surface modifier in the composite composition is polymerized or crosslinked via a reaction catalyst to increase the degree of bonding between the polyoxynoxy resins or the polyoxyxylene resin and the surface modifier. (degree of polymerization).

又，在此成形體或充填物中殘留有機溶劑時，揮發除去此有機溶劑。 Further, when the organic solvent remains in the molded body or the filler, the organic solvent is volatilized and removed.

藉此，此成形體或充填物在從模具或容器脫離後，會成為即使對其施加外力也可維持一定形狀的形態。 Thereby, after the molded body or the filler is detached from the mold or the container, it can be maintained in a constant shape even if an external force is applied thereto.

藉由上述內容，可得到無缺陷、且光學持性、機械特性優異、並具有高熱安定性或化學安定性之本實施形態的透明複合體。 According to the above, a transparent composite of the present embodiment which is free from defects, has excellent optical properties, excellent mechanical properties, and has high thermal stability or chemical stability can be obtained.

又，本實施形態的製造方法中，「將複合組成物固化後予以成形為預定之形狀的方法」是如以下所述。 Further, in the production method of the present embodiment, the "method of forming the composite composition into a predetermined shape after curing" is as follows.

首先，將本實施形態的複合組成物固化，而得到複合組成物的固化物(未成形的透明複合體)。就固化方法而言，只要將複合組成物直接在室溫(25℃左右)中或是加溫至預定溫度(室溫至150℃，更佳是80℃至150℃)而靜置預定時間，對於此複合組成物中之聚矽氧樹脂或表面修飾劑經由反應觸媒而進行聚合或交聯等反應，以提高聚矽氧樹脂彼此或聚矽氧樹脂與表面修飾劑間之結合度(聚合度)即可。 First, the composite composition of the present embodiment is cured to obtain a cured product (unformed transparent composite) of the composite composition. In terms of the curing method, the composite composition is allowed to stand still at room temperature (about 25 ° C) or at a predetermined temperature (room temperature to 150 ° C, more preferably 80 ° C to 150 ° C) for a predetermined time. The polyfluorene oxide resin or the surface modifying agent in the composite composition is subjected to polymerization or crosslinking reaction via a reaction catalyst to increase the degree of bonding between the polyoxynoxy resins or the polyoxyxylene resin and the surface modifier (polymerization). Degree).

又，在殘留有機溶劑時，也以揮發除去此有機溶劑為宜。 Further, when the organic solvent remains, it is preferred to remove the organic solvent by volatilization.

此固化物係即使經施加外力也可維持一定形狀的形態。 This cured product maintains a shape of a certain shape even if an external force is applied.

其次，將此固化物藉由切削或脫模等機械加工法，而成形為必要之形狀。本實施形態的聚矽氧樹脂在硬化後也 有柔軟性，可容易地加工。 Next, the cured product is formed into a necessary shape by a machining method such as cutting or demolding. The polyoxynoxy resin of the present embodiment is also cured after curing It is soft and can be easily processed.

再者，在加工後之成型體中，亦可藉由提高聚矽氧樹脂彼此或聚矽氧樹脂與表面修飾劑間之結合度(聚合度)、或是除去殘留之有機溶劑，而更加進行固化。 Further, in the molded body after processing, it is also possible to further improve the degree of bonding (degree of polymerization) between the polyoxynoxy resins or the polyoxyxylene resin and the surface modifier, or to remove the residual organic solvent. Cured.

藉由以上內容，可得到無缺陷、且光學持性、機械特性優異、並具有高熱安定性或化學安定性之本實施形態的透明複合體。 According to the above, a transparent composite of the present embodiment which is free from defects, has excellent optical properties, excellent mechanical properties, and has high thermal stability or chemical stability can be obtained.

將此透明複合體適用於不將透明性視為問題之領域中時，因為沒必要確保透明性，故不需將使用之無機氧化物粒子的平均分散粒徑限制在1nm以上且20nm以下。 When the transparent composite is applied to a field where transparency is not considered to be a problem, since it is not necessary to ensure transparency, it is not necessary to limit the average dispersed particle diameter of the inorganic oxide particles to be used to 1 nm or more and 20 nm or less.

例如，在只以提高含有無機氧化物粒子與聚矽氧樹脂之複合體的表面硬度作為目的時，亦可使用平均分散粒徑大於20nm之粒子，例如100nm的無機氧化物粒子。 For example, in order to increase the surface hardness of the composite containing the inorganic oxide particles and the polyoxyxylene resin, particles having an average dispersed particle diameter of more than 20 nm, for example, 100 nm of inorganic oxide particles may be used.

即使在如此之情形下，藉由適用本實施形態的複合組成物之製造方法，仍可製作使複合組成物中的無機氧化物粒子之分散性高，且可製作具有良好物性之成形體或充填物的複合組成物。 Even in such a case, by applying the method for producing a composite composition of the present embodiment, the dispersion of the inorganic oxide particles in the composite composition can be made high, and a molded body or a filling having good physical properties can be produced. a composite composition of matter.

實施例 Example

以下，根據實施例及比較例而具體說明本發明，但本發明並不侷限於此等實施例。在不脫離本發明之主旨之範圍內，可做結構之加成、省略、替換、及其他之變更。 Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the examples. Additions, omissions, substitutions, and other modifications of the structure may be made without departing from the spirit of the invention.

實施例1 Example 1

在40L(公升)的純水中溶解有2615g之氧氯化鋯8水合鹽而成的鋯鹽溶液中，將在20L的純水中溶解有344g之 28%氨水而成的稀氨水一面攪拌一面加入，而調製氧化鋯前驅物漿液(slurry)。 In a zirconium salt solution in which 2615 g of zirconium oxychloride 8 hydrate salt is dissolved in 40 L (liter) of pure water, 344 g of the solution is dissolved in 20 L of pure water. A dilute aqueous ammonia solution of 28% ammonia water was added while stirring to prepare a zirconia precursor slurry.

其次，在此漿液中，將在5L的純水中溶解有300g之硫酸鈉而成的硫酸鈉水溶液一面攪拌一面加入，此時之硫酸鈉的添加量，相對於鋯鹽溶液中之鋯離子的氧化鋯換算值，是30質量%。 Next, in this slurry, a sodium sulfate aqueous solution obtained by dissolving 300 g of sodium sulfate in 5 L of pure water is added while stirring, and the amount of sodium sulfate added at this time is relative to the zirconium ion in the zirconium salt solution. The zirconia conversion value is 30% by mass.

其次，將此混合物使用乾燥器在大氣中於130℃下乾燥24小時，得到固形物。 Next, this mixture was dried in the air at 130 ° C for 24 hours using a drier to obtain a solid matter.

其次，將此固形物使用自動乳鉢粉碎後，使用電爐，在大氣中於500℃下燒成1小時。 Next, this solid matter was pulverized using an automatic mortar, and fired in the air at 500 ° C for 1 hour in an electric furnace.

接著，將此燒成物投入純水中，攪拌成漿液狀後，使用離心分離器進行洗淨，將添加之硫酸鈉充分除去後，以乾燥器乾燥，得到氧化鋯粒子。 Then, the fired product was poured into pure water, stirred to form a slurry, and then washed with a centrifugal separator, and the added sodium sulfate was sufficiently removed, and then dried in a dryer to obtain zirconia particles.

其次，在此氧化鋯粒子10g中加入甲苯85g、己酸5g並加以混合，將氧化鋯粒子的表面經由屬於配位基的己酸而修飾。之後，進行分散處理，調製氧化鋯透明分散液。 Next, 85 g of toluene and 5 g of hexanoic acid were added to 10 g of the zirconia particles and mixed, and the surface of the zirconia particles was modified via hexanoic acid belonging to a ligand. Thereafter, dispersion treatment was carried out to prepare a transparent dispersion of zirconia.

接著，在該氧化鋯透明分散液100g中，加入作為單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物的單縮水甘油基醚末端聚二甲基矽氧烷(PDMS-G：數平均分子量是5000：Aldrich公司製)10g、二月桂酸二丁基錫0.01g，於回流下進行表面修飾。 Next, in 100 g of the zirconia transparent dispersion, a monoglycidyl ether terminal polydimethyl siloxane (PDMS-) was added as a polydimethyl methoxy siloxane backbone polymer having one functional group at one end. G: a number average molecular weight: 5,000: 10 g of Aldrich Co., Ltd., and 0.01 g of dibutyltin dilaurate, and surface modification was carried out under reflux.

反應終止後，以蒸發器除去溶劑，藉由重覆進行甲醇洗淨與離心分離，而將從氧化鋯粒子脫離之己酸、及未反應之單縮水甘油基醚末端聚二甲基矽氧烷去除。回收之表 面修飾氧化鋯粒子(亦即，經表面修飾之氧化鋯粒子)是15g。 After the reaction is terminated, the solvent is removed by an evaporator, and methanol is washed and centrifuged repeatedly to remove hexanoic acid, which is detached from the zirconia particles, and unreacted monoglycidyl ether terminal polydimethyl siloxane. Remove. Recycling table The surface modified zirconia particles (i.e., the surface modified zirconia particles) were 15 g.

將得到之表面處理氧化鋯粒子以質子NMR(重氯仿中)測定之結果，2.6至3.5ppm附近之因縮水甘油基所致的訊號強度，係比起單縮水甘油基醚末端聚二甲基矽氧烷單獨之情形而為大幅減少。由此結果可判定，單縮水甘油基醚末端聚二甲基矽氧烷係發生環氧基之開環及與氧化鋯粒子之結合。 As a result of measuring the surface-treated zirconia particles by proton NMR (in heavy chloroform), the signal intensity due to the glycidyl group in the vicinity of 2.6 to 3.5 ppm is higher than that of the monoglycidyl ether terminal polydimethyl hydrazine. The oxyalkylene is substantially reduced in the case of isolation. From this result, it was judged that the monoglycidyl ether terminal polydimethyl siloxane was subjected to ring opening of an epoxy group and bonding to zirconia particles.

將此表面修飾氧化鋯粒子15g再分散到甲苯35g後，加入作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131(Gelest公司製)14.1g、作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151(Gelest公司製)0.9g，更進一步加入作為反應觸媒之室溫硬化用的鉑二乙烯基四甲基二矽氧烷SIP6830.3(Gelest公司製)6mg，得到實施例1之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物。 After dispersing 15 g of the surface-modified zirconia particles in 35 g of toluene, 14.1 g of a side chain vinyl-dimethylpolyfluorene VDT-131 (manufactured by Gelest Co., Ltd.) as a vinyl modified polyfluorene was added as a hydrogen reform. 0.1 g of methyl hydrogen-dimethylpolyfluorene HMS-151 (manufactured by Gelest Co., Ltd.), which is a polyoxyl group, and further added platinum divinyltetramethyldioxane for room temperature hardening as a reaction catalyst. 6 mg of SIP6830.3 (manufactured by Gelest Co., Ltd.) was obtained as a surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 1.

其次，將此表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物攪拌溶解後，流入以玻璃板組裝成之模具中，於40℃真空下除去有機溶劑，並進行硬化反應，得到實施例1的厚度為1mm之透明複合體。 Then, the surface-modified zirconia particle-polyoxymethylene resin composite composition was stirred and dissolved, and then poured into a mold assembled in a glass plate, and the organic solvent was removed under vacuum at 40 ° C to carry out a hardening reaction to obtain the Example 1 A transparent composite having a thickness of 1 mm.

該透明複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the transparent composite was 25% by mass.

將所得到的實施例1透明複合體之截面，使用場發射型穿透電子顯微鏡JEM-2100F(日本電子公司製)觀察，測定隨機選出100個粒子之粒徑，將此平均值當作透明複合體內之氧化鋯粒子的平均分散粒徑。該測定結果，平均分 散粒徑是7nm。 The cross section of the obtained transparent composite of Example 1 was observed by a field emission type electron microscope JEM-2100F (manufactured by JEOL Ltd.), and the particle diameter of 100 particles was randomly selected, and the average value was regarded as a transparent composite. The average dispersed particle size of the zirconia particles in the body. Average of the test results The bulk particle size is 7 nm.

由此測定結果而作下述結論：實施例1之複合組成物中之氧化鋯粒子的平均分散粒徑亦為7nm或其以下。 From the results of the measurement, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 1 was also 7 nm or less.

又，對於所得到的實施例1之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 1, since the platinum component equivalent to the amount added as the reaction catalyst was detected, it was confirmed that the transparent composite of the present invention was obtained.

實施例2 Example 2

除了分別將氧化鋯粒子從10g(25質量%)改成14g(35質量%)，並將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131從14.1g(47質量%)改成8.4g(28質量%)，將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151從0.9g(3質量%)改成0.6g(2質量%)之外，其餘根據實施例1操作，得到實施例2之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的透明複合體。 In addition to the zirconia particles were changed from 10 g (25 mass%) to 14 g (35 mass%), respectively, and the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyfluorene oxygen was used from 14.1 g. (47% by mass) was changed to 8.4 g (28% by mass), and methyl hydrogen-dimethylpolyfluorene HMS-151, which is a hydrogen-modified polyfluorene oxide, was changed from 0.9 g (3 mass%) to 0.6 g ( The surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 2 and the transparent composite body having a thickness of 1 mm were obtained by the operation of Example 1 except for 2% by mass.

該透明複合體之氧化鋯粒子的含有率是35質量%。 The content of the zirconia particles in the transparent composite was 35% by mass.

將所得之實施例2之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是8nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 2 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 8 nm.

由此結果而作下述結論：實施例2之複合組成物中的氧化鋯粒子之平均分散粒徑亦為8nm或其以下。 From the results, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 2 was also 8 nm or less.

又，對於所得到的實施例2之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 2, since the platinum component equivalent to the amount added as the reaction catalyst was detected, it was confirmed that the transparent composite of the present invention was obtained.

實施例3 Example 3

除了分別將氧化鋯粒子從10g(25質量%)改成16g(40質量%)，並將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131從14.1g(47質量%)改成5.7g(19質量%)，將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151從0.9g(3質量%)改成0.3g(1質量%)，將作為反應觸媒之鉑二乙烯基四甲基二矽氧烷SIP6830.3從6mg(0.02質量%)改成3mg(0.01質量%)之外，其餘根據實施例1操作，得到實施例3之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的透明複合體。 In addition to the zirconia particles were changed from 10 g (25 mass%) to 16 g (40 mass%), respectively, and the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyfluorene oxygen was used from 14.1 g. (47% by mass) was changed to 5.7 g (19% by mass), and methyl hydrogen-dimethylpolyfluorene HMS-151 as hydrogen-modified polyfluorene was changed from 0.9 g (3% by mass) to 0.3 g ( 1% by mass), except that platinum divinyltetramethyldioxane SIP6830.3 as a reaction catalyst was changed from 6 mg (0.02% by mass) to 3 mg (0.01% by mass), and the rest was operated according to Example 1, A surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 3 and a transparent composite having a thickness of 1 mm were obtained.

該透明複合體之氧化鋯粒子的含有率是40質量%。 The content of the zirconia particles in the transparent composite was 40% by mass.

將所得之實施例3之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是10nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 3 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 10 nm.

由此結果而作下述結論：實施例3之複合組成物中的氧化鋯粒子之平均分散粒徑亦為10nm或其以下。 From the results, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 3 was also 10 nm or less.

又，對於所得到的實施例3之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 3, the platinum component of the same amount as that added as the reaction catalyst was detected, and thus the transparent composite of the present invention was confirmed.

實施例4 Example 4

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131從14.1g(47質量%)改成11.7g(39質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-031(Gelest公司製)3.3g(11質量%)之外，其餘根據實施例1 操作，得到實施例4之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的透明複合體。 In addition to the side-chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl-modified polyfluorene oxygen, respectively, was changed from 14.1 g (47 mass%) to 11.7 g (39 mass%), and was modified as hydrogen. 0.9 g (3 mass%) of polyoxymethane-methyl hydrogen-dimethyl polyfluorene HMS-151 was changed to methyl hydrogen-dimethyl polyfluorene HMS-031 (manufactured by Gelest) 3.3 g (11 mass) Other than %), according to the embodiment 1 The surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 4 and a transparent composite having a thickness of 1 mm were obtained.

該透明複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the transparent composite was 25% by mass.

將所得之實施例4之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是7nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 4 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 7 nm.

由此結果而作下述結論：實施例4的複合組成物中的氧化鋯粒子之平均分散粒徑亦為7nm或其以下。 From the results, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 4 was also 7 nm or less.

又，對於所得到的實施例4之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 4, the platinum component of the same amount as that added as the reaction catalyst was detected, and thus the transparent composite of the present invention was confirmed.

實施例5 Example 5

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131之14.1g(47質量%)改成側鏈乙烯基-二甲基聚矽氧烷VDT-731(Gelest公司製)4.8g(16質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-031之10.2g(34質量%)之外，其餘根據實施例1操作，得到實施例5之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的透明複合體。 In addition to 14.1 g (47% by mass) of the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyfluorene oxygen, a side chain vinyl-dimethyl polyoxane VDT- 731 (manufactured by Gelest Co., Ltd.) 4.8 g (16 mass%), and 0.9 g (3 mass%) of methyl hydrogen-dimethyl polyfluorene HMS-151 as a hydrogen-modified polyfluorene oxide was changed to methyl hydrogen. The surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 5 was obtained by the operation of Example 1 except that 10.2 g (34% by mass) of dimethylpolyfluorene HMS-031 was used, and the thickness was 1 mm. Transparent complex.

該透明複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the transparent composite was 25% by mass.

將所得之實施例5之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是7nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 5 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 7 nm.

由此結果而作下述結論：實施例5的複合組成物中的氧化鋯粒子之平均分散粒徑亦為7nm或其以下。 From this result, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 5 was also 7 nm or less.

又，對於所得到的實施例5之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 5, since the platinum component equivalent to the amount added as the reaction catalyst was detected, it was confirmed that the transparent composite of the present invention was obtained.

實施例6 Example 6

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131之14.1g(47質量%)改成兩末端乙烯基-二甲基聚矽氧DMS-V21(Gelest公司製)13.5g(45質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-301(Gelest公司製)1.5g(5質量%)之外，其餘根據實施例1操作，得到實施例6之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的透明複合體。 In addition to 14.1 g (47% by mass) of the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyoxyl oxide, respectively, a two-terminal vinyl-dimethyl polyfluorene DMS-V21 was changed. (Gelest), 13.5 g (45% by mass), and 0.9 g (3% by mass) of methyl hydrogen-dimethylpolyfluorene HMS-151 as hydrogen-modified polyfluorene was changed to methyl hydrogen- The surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 6 was obtained by the operation of Example 1 except that 1.5 g (5 mass%) of dimethylpolyfluorene HMS-301 (manufactured by Gelest) was used. A transparent composite having a thickness of 1 mm.

該透明複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the transparent composite was 25% by mass.

將所得之實施例6之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是10nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 6 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 10 nm.

由此結果而作下述結論：實施例6的複合組成物中的氧化鋯粒子之平均分散粒徑亦為10nm或其以下。 From the results, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 6 was also 10 nm or less.

又，對於所得到的實施例6之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 6, since a platinum component equivalent to the amount added as a reaction catalyst was detected, it was confirmed that the transparent composite of the present invention was obtained.

實施例7 Example 7

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131之14.1g(47質量%)改成兩末端乙烯基-二甲基聚矽氧DMS-V22(Gelest公司製)14.7g(49質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-301之0.3g(1質量%)之外，其餘根據實施例1操作，得到實施例7之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的透明複合體。 In addition to 14.1 g (47% by mass) of the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyoxyl oxide, respectively, a two-terminal vinyl-dimethyl polyfluorene DMS-V22 was changed. (manufactured by Gelest Co., Ltd.) 14.7 g (49% by mass), and 0.9 g (3% by mass) of methyl hydrogen-dimethylpolyfluorene HMS-151 as hydrogen-modified polyfluorene was changed to methyl hydrogen- The surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 7 and the thickness of 1 mm were obtained according to the operation of Example 1, except that 0.3 g (1% by mass) of dimethylpolyfluorene HMS-301 was used. Transparent composite.

該透明複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the transparent composite was 25% by mass.

將所得到之實施例7之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是10nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 7 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 10 nm.

由此結果而作下述結論：實施例7的複合組成物中的氧化鋯粒子之平均分散粒徑亦為10nm或其以下。 From this result, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 7 was also 10 nm or less.

又，對於所得到的實施例7之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 7, since the platinum component equivalent to the amount added as the reaction catalyst was detected, it was confirmed that the transparent composite of the present invention was obtained.

實施例8 Example 8

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131從14.1g(47質量%)改成14.4g(48質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-301之0.6g(2質量%)之外，其餘根據實施例1的操作，得到實施例8之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及 厚度為1mm的透明複合體。 In addition to the side-chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl-modified polyfluorene oxygen, respectively, was changed from 14.1 g (47 mass%) to 14.4 g (48 mass%), and was modified as hydrogen. 0.9 g (3 mass%) of polyoxymethane-methyl hydrogen-dimethyl polyfluorene HMS-151 was changed to 0.6 g (2 mass%) of methyl hydrogen-dimethyl polyfluorene HMS-301 According to the operation of Example 1, the surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 8 and A transparent composite having a thickness of 1 mm.

該透明複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the transparent composite was 25% by mass.

將所得之實施例8之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是7nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 8 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 7 nm.

由此結果而作下述結論：實施例8之複合組成物中之氧化鋯粒子之平均分散粒徑亦為7nm或其以下。 From the results, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 8 was also 7 nm or less.

又，對於所得到的實施例8之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 8, since a platinum component equivalent to the amount added as a reaction catalyst was detected, it was confirmed that the transparent composite of the present invention was obtained.

實施例9 Example 9

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131之14.1g(47質量%)改成側鏈乙烯基-二甲基聚矽氧VDT-731之11.4g(38質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-301之3.6g(12質量%)之外，其餘根據實施例1操作，得到實施例9之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的透明複合體。 In addition to 14.1 g (47% by mass) of the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyfluorene oxygen, a side chain vinyl-dimethyl polyoxyl VDT-731 was separately changed. 11.4 g (38% by mass), and changed 0.9 g (3 mass%) of methyl hydrogen-dimethyl polyfluorene HMS-151 as a hydrogen-modified polyfluorene to methyl hydrogen-dimethyl poly A surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 9 and a transparent composite having a thickness of 1 mm were obtained in the same manner as in Example 1 except that 3.6 g (12% by mass) of the oxime HMS-301 was used.

該透明複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the transparent composite was 25% by mass.

將所得之實施例9之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是7nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 9 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 7 nm.

由此結果而作下述結論：實施例9的複合組成物中的 氧化鋯粒子之平均分散粒徑亦為7nm或其以下。 From this result, the following conclusion was drawn: in the composite composition of Example 9. The average dispersed particle diameter of the zirconia particles is also 7 nm or less.

又，對於所得到的實施例9之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 9, since a platinum component equivalent to the amount added as a reaction catalyst was detected, it was confirmed that the transparent composite of the present invention was obtained.

實施例10 Example 10

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131之14.1g(47質量%)改成兩末端乙烯基-二甲基聚矽氧DMS-V22之14.7g(49質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-301之0.3g(1質量%)，將作為反應觸媒之鉑二乙烯基四甲基二矽氧烷SIP 6830.3改成鉑環乙烯基甲基矽氧烷SIP 6832.2(Gelest公司製)之外，其餘根據實施例1操作，得到實施例10之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的透明複合體。 In addition to 14.1 g (47% by mass) of the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyoxyl oxide, respectively, a two-terminal vinyl-dimethyl polyfluorene DMS-V22 was changed. 14.7 g (49% by mass), and 0.9 g (3 mass%) of methyl hydrogen-dimethyl polyfluorene HMS-151 as a hydrogen-modified polyfluorene oxide was changed to methyl hydrogen-dimethyl poly 0.3 g (1% by mass) of deuterium HMS-301, and converted platinum divinyltetramethyldioxane SIP 6830.3 as a reaction catalyst to platinum cyclovinylmethyl decane SIP 6832.2 (Gelest) Except for the operation of Example 1, the surface-modified zirconia particle-polyoxymethylene resin composite composition of Example 10 and a transparent composite having a thickness of 1 mm were obtained.

該透明複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the transparent composite was 25% by mass.

將所得之實施例10之透明複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是9nm。 The particle diameter of the zirconia particles in the obtained transparent composite of Example 10 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 9 nm.

由此結果而作下述結論：實施例10的複合組成物中的氧化鋯粒子之平均分散粒徑亦為9nm或其以下。 From the results, it was concluded that the average dispersed particle diameter of the zirconia particles in the composite composition of Example 10 was also 9 nm or less.

又，對於所得到的實施例10之透明複合體進行元素分析的結果，由於可檢測出與作為反應觸媒所添加之量同等量的鉑成分，故確認得到本發明之透明複合體。 Further, as a result of elemental analysis of the obtained transparent composite of Example 10, the platinum component of the same amount as that added as the reaction catalyst was detected, and thus the transparent composite of the present invention was confirmed.

比較例1 Comparative example 1

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131之14.1g(47質量%)改成兩末端乙烯基-二甲基聚矽氧DMS-V21之8.7g(29質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-031之6.3g(21質量%)之外，其餘根據實施例1操作，得到比較例1的表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的複合體。 In addition to 14.1 g (47% by mass) of the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyoxyl oxide, respectively, a two-terminal vinyl-dimethyl polyfluorene DMS-V21 was changed. 8.7 g (29 mass%), and 0.9 g (3 mass%) of methyl hydrogen-dimethyl polyfluorene HMS-151 as a hydrogen-modified polyfluorene oxide was changed to methyl hydrogen-dimethyl poly A surface-modified zirconia particle-polyoxymethylene resin composite composition of Comparative Example 1 and a composite having a thickness of 1 mm were obtained in the same manner as in Example 1 except that 6.3 g (21% by mass) of the oxime HMS-031 was used.

該複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the composite was 25% by mass.

將所得到的比較例1的複合體中之氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是35nm。 The particle diameter of the zirconia particles in the obtained composite of Comparative Example 1 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 35 nm.

比較例2 Comparative example 2

除了分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131之14.1g(47質量%)改成兩末端乙烯基-二甲基聚矽氧DMS-V22之13.2g(44質量%)，並將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151之0.9g(3質量%)改成甲基氫-二甲基聚矽氧HMS-031之1.8g(6質量%)之外，其餘根據實施例1操作，得到比較例2之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的複合體。 In addition to 14.1 g (47% by mass) of the side chain vinyl-dimethyl polyfluorene VDT-131 as a vinyl modified polyoxyl oxide, respectively, a two-terminal vinyl-dimethyl polyfluorene DMS-V22 was changed. 13.2 g (44% by mass), and changed 0.9 g (3% by mass) of methyl hydrogen-dimethyl polyfluorene HMS-151 as a hydrogen-modified polyfluorene to methyl hydrogen-dimethyl poly A surface-modified zirconia particle-polyoxymethylene resin composite composition of Comparative Example 2 and a composite having a thickness of 1 mm were obtained in the same manner as in Example 1 except that 1.8 g (6 mass%) of the deuterium HMS-031 was used.

該複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the composite was 25% by mass.

將所得到的比較例2之複合體中的氧化鋯粒子的粒 徑，以與實施例1同樣方式測定，結果，平均分散粒徑是42nm。 The granules of the zirconia particles in the obtained composite of Comparative Example 2 The diameter was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 42 nm.

比較例3 Comparative example 3

在以與實施例1同樣方式製作的氧化鋯粒子10g中，加入甲苯85g、己酸5g並混合，將氧化鋯粒子之表面經由屬於配位基的己酸而修飾。之後，進行分散處理，調製氧化鋯透明分散液。 To 10 g of the zirconia particles produced in the same manner as in Example 1, 85 g of toluene and 5 g of hexanoic acid were added and mixed, and the surface of the zirconia particles was modified via hexanoic acid belonging to a ligand. Thereafter, dispersion treatment was carried out to prepare a transparent dispersion of zirconia.

反應終止後，以蒸發器除去溶劑，藉由重覆進行丙酮洗淨與離心分離，除去氧化鋯粒子與未反應之己酸。回收到的經屬於配位基之己酸而修飾表面之氧化鋯粒子是11g。 After the reaction was terminated, the solvent was removed by an evaporator, and acetone washing and centrifugation were repeated by repeated to remove zirconia particles and unreacted hexanoic acid. The recovered zirconia particles modified by the hexanoic acid belonging to the ligand were 11 g.

除了使用該經己酸修飾之氧化鋯粒子10g(25質量%)作為氧化鋯粒子，並分別將作為乙烯基改質聚矽氧之側鏈乙烯基-二甲基聚矽氧VDT-131從14.1g(47質量%)改成18.8g(63質量%)，將作為氫改質聚矽氧之甲基氫-二甲基聚矽氧HMS-151從0.9g(3質量%)改成1.2g(4質量%)，將作為反應觸媒之鉑二乙烯基四甲基二矽氧烷SIP6830.3從6mg(0.02質量%)改成9mg(0.03質量%)之外，其餘根據實施例1操作，得到比較例3之表面修飾氧化鋯粒子-聚矽氧樹脂複合組成物及厚度為1mm的複合體。 In addition to using the hexanoic acid-modified zirconia particles 10 g (25 mass%) as zirconia particles, and respectively, as a vinyl-modified polyfluorene-oxygen side chain vinyl-dimethyl polyfluorene VDT-131 from 14.1, respectively. g (47% by mass) was changed to 18.8 g (63% by mass), and methyl hydrogen-dimethylpolyfluorene HMS-151 as hydrogen-modified polyfluorene was changed from 0.9 g (3% by mass) to 1.2 g. (4% by mass), the platinum divinyltetramethyldioxane SIP6830.3 as a reaction catalyst was changed from 6 mg (0.02% by mass) to 9 mg (0.03% by mass), and the rest was operated according to Example 1. A surface-modified zirconia particle-polyoxymethylene resin composite composition of Comparative Example 3 and a composite having a thickness of 1 mm were obtained.

該複合體之氧化鋯粒子的含有率是25質量%。 The content of the zirconia particles in the composite was 25% by mass.

將所得到的比較例3之複合體中的氧化鋯粒子的粒徑，以與實施例1同樣方式測定，結果，平均分散粒徑是45nm。 The particle diameter of the zirconia particles in the obtained composite of Comparative Example 3 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 45 nm.

[評估] [assessment]

對於實施例1至10之各透明複合體及比較例1至3之各複合體，藉由下述裝置或方法進行透明性、折射率、及耐久性之評估。 For each of the transparent composites of Examples 1 to 10 and the composites of Comparative Examples 1 to 3, the evaluation of transparency, refractive index, and durability was carried out by the following apparatus or method.

(1)透明性 (1) Transparency

使用分光光度計(日本分光公司製)測定可見光線之穿透率。 The transmittance of visible light was measured using a spectrophotometer (manufactured by JASCO Corporation).

在此，測定透明複合體(或是複合體)的厚度方向(L=1mm)的可見光線之穿透率，將可見光線之穿透率在80%以上者當作「○」，將未逹80%者當作「×」。 Here, the transmittance of the visible light in the thickness direction (L=1 mm) of the transparent composite (or the composite) is measured, and the transmittance of the visible light is 80% or more as "○", and the attempt is made. 80% of them are treated as "X".

(2)折射率 (2) Refractive index

根據日本工業規格JIS K 7132「塑膠之折射率測定方法」，藉由阿貝折射計(Abbe refractometer)來測定。 According to Japanese Industrial Standard JIS K 7132 "Method for Measuring Refractive Index of Plastics", it is measured by an Abbe refractometer.

在此，將未添加氧化鋯粒子之樹脂單獨者當作基準，將折射率提高至0.03以上的情形當作「○」，將折射率僅提高至未逹0.03的情形當作「×」。 Here, the resin in which the zirconia particles are not added is used as a standard, and the case where the refractive index is increased to 0.03 or more is regarded as "○", and the case where the refractive index is only increased to not more than 0.03 is regarded as "x".

(3)耐久性 (3) Durability

將透明複合體(或是複合體)在溫度150℃之環境下放置24小時後，取出，以目視觀察透明複合體(或是複合體)之外觀，沒有黃變者當作「○」，已黃變者當作「×」。 The transparent composite (or composite) was allowed to stand in an environment at a temperature of 150 ° C for 24 hours, and then taken out to visually observe the appearance of the transparent composite (or composite), and no yellowing was regarded as "○". The yellower is treated as "X".

將實施例1至10及比較例1至2之各複合組成物之組成及透明複合體(或是複合體)的評估結果表示在表1中。 The evaluation results of the compositions of the composite compositions of Examples 1 to 10 and Comparative Examples 1 to 2 and the transparent composite (or composite) are shown in Table 1.

由表1可知，實施例1至10之各透明複合體在透明性、折射率及耐久性之全部特點上皆為優良者。 As is clear from Table 1, each of the transparent composites of Examples 1 to 10 is excellent in all of the characteristics of transparency, refractive index, and durability.

另一方面，比較例1、2之複合體，其可見光線之穿透率是0%至20%而為極低，此外，無法測定折射率。 On the other hand, in the composites of Comparative Examples 1 and 2, the visible light transmittance was extremely low from 0% to 20%, and the refractive index could not be measured.

推測其理由是：由於氫改質聚矽氧及乙烯基改質聚矽氧之交聯密度皆小，故無機氧化物粒子的凝集/相分離速度變得比聚矽氧樹脂之硬化速度還快，結果，導致在無機氧化物粒子與聚矽氧樹脂硬化時失去透明性。 The reason is presumed to be that since the cross-linking density of the hydrogen-modified polyfluorene and the vinyl-modified poly-n-oxygen is small, the aggregation/phase separation speed of the inorganic oxide particles becomes faster than the hardening speed of the polyoxynoxy resin. As a result, the transparency is lost when the inorganic oxide particles and the polyoxymethylene resin are hardened.

又，比較例3之複合體，其可見光線之穿透率是10%以下而為極低，且無法測定到折射率。推測其理由是：由於無機氧化物粒子的表面修飾不充分，故在無機氧化物粒子與聚矽氧樹脂之複合組成物中，無機氧化物粒子會凝集，結果，無法獲得複合體中之透明性。再者，關於耐久性，在150℃放置24小時後，由於看到微黃變，故確認到由己酸所致之變色的影響。 Further, in the composite of Comparative Example 3, the visible light transmittance was extremely low at 10% or less, and the refractive index could not be measured. The reason is presumed to be that the inorganic oxide particles are aggregated in the composite composition of the inorganic oxide particles and the polyfluorene oxide resin because the surface modification of the inorganic oxide particles is insufficient. As a result, the transparency in the composite cannot be obtained. . Further, regarding the durability, after standing at 150 ° C for 24 hours, the effect of discoloration caused by hexanoic acid was confirmed due to the slight yellowing.

[產業上之可利用性] [Industrial availability]

本發明可提供一種無機氧化物粒子與聚矽氧樹脂的複合組成物及透明複合體，其中，在將可提升折射率、機械特性及氣體阻隔性的無機氧化物粒子分散到聚矽氧樹脂中時，係分散性高，並且，防止硬化時之相分離/白化，可確保透明性。 The present invention can provide a composite composition of an inorganic oxide particle and a polyoxyxylene resin, and a transparent composite in which inorganic oxide particles capable of improving refractive index, mechanical properties, and gas barrier properties are dispersed in a polyoxyl resin. In this case, the dispersibility is high, and phase separation/whitening at the time of hardening is prevented, and transparency is ensured.

本發明的無機氧化物粒子與聚矽氧樹脂之複合組成物，係將無機氧化物粒子分散到聚矽氧樹脂中而成的複合組成物，其至少含有無機氧化物粒子、聚矽氧樹脂與反應 觸媒；其中，無機氧化物粒子是藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾，同時平均分散粒徑為1nm以上且20nm以下的無機氧化物粒子。藉此，可得到維持由無機氧化物粒子與聚矽氧樹脂複合而成之複合體之透明性、耐熱性及耐光性，且亦已控制折射率的透明複合體。因此，當然可利用在半導體發光元件(LED)密封材、液晶顯示裝置用基板、有機EL顯示裝置用基板、彩色濾光片用基板、觸控面板用基板、太陽電池用基板等光學薄片、透明板、光學透鏡、光學元件、光波導、接著劑等中，並且，其在此外之各式各樣的工業領域中也有很大之可利用性。 The composite composition of the inorganic oxide particles and the polyfluorene oxide resin of the present invention is a composite composition obtained by dispersing inorganic oxide particles in a polyfluorene oxide resin, and at least contains inorganic oxide particles, polyfluorene oxide resin, and reaction a catalyst; wherein the inorganic oxide particles are surface-modified by combining a polydimethyl methoxy siloxane backbone polymer having a functional group at one end, and the inorganic particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less Oxide particles. Thereby, a transparent composite in which the transparency, heat resistance, and light resistance of the composite obtained by combining the inorganic oxide particles and the polyfluorene oxide resin are maintained, and the refractive index is also controlled can be obtained. Therefore, it is of course possible to use optical sheets such as a semiconductor light-emitting element (LED) sealing material, a liquid crystal display device substrate, an organic EL display device substrate, a color filter substrate, a touch panel substrate, and a solar cell substrate, and the like. Plates, optical lenses, optical elements, optical waveguides, adhesives, and the like, and they are also highly available in a wide variety of industrial fields.

Claims (8)

一種無機氧化物粒子與聚矽氧樹脂(silicone resin)的複合組成物，該複合組成物係至少含有無機氧化物粒子、聚矽氧樹脂與反應觸媒的複合組成物；其中，該無機氧化物粒子是藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾，同時平均分散粒徑為1nm以上且20nm以下的無機氧化物粒子；並以1質量%以上且90質量%以下含有前述無機氧化物粒子；前述聚矽氧樹脂含有乙烯基改質聚矽氧及氫改質聚矽氧；前述反應觸媒含有矽氫化反應觸媒。 a composite composition of inorganic oxide particles and a silicone resin, the composite composition comprising at least inorganic oxide particles, a composite composition of a polyoxyxylene resin and a reaction catalyst; wherein the inorganic oxide The particles are surface-modified by combining a polydimethyl methoxy oxane backbone polymer having a functional group at one end, and an inorganic oxide particle having an average dispersed particle diameter of 1 nm or more and 20 nm or less; The above inorganic oxide particles are contained in an amount of not less than 90% by mass; the polyfluorene oxide resin contains a vinyl-modified polyfluorene oxide and a hydrogen-modified polyfluorene oxide; and the reaction catalyst contains a hydrogenation-reactive catalyst. 如申請專利範圍第1項所述之無機氧化物粒子與聚矽氧樹脂的複合組成物，其中，前述聚二甲基矽氧烷骨幹聚合物是單縮水甘油基醚末端聚二甲基矽氧烷及/或單羥基醚末端聚二甲基矽氧烷。 The composite composition of the inorganic oxide particles and the polyoxyxylene resin according to claim 1, wherein the polydimethyl methoxy siloxane backbone polymer is monoglycidyl ether terminal polydimethyl oxime Alkane and/or monohydroxy ether end polydimethyl methoxy alkane. 如申請專利範圍第1或2項所述之無機氧化物粒子與聚矽氧樹脂的複合組成物，其中，前述乙烯基改質聚矽氧係選自由兩末端乙烯基-二甲基聚矽氧、兩末端乙烯基二苯基-二甲基聚矽氧、兩末端乙烯基-苯基甲基聚矽氧、兩末端乙烯基-二乙基聚矽氧、側鏈乙烯基-二甲基聚矽氧、乙烯基甲基聚矽氧、乙烯基甲氧基聚矽氧、乙烯基樹脂分散物所成群組中之1種或2種以上。 The composite composition of the inorganic oxide particles and the polyoxyxylene resin according to claim 1 or 2, wherein the vinyl modified polyfluorene oxide is selected from the group consisting of vinyl-dimethylpolyoxyl at both ends. , two-terminal vinyl diphenyl-dimethyl polyfluorene oxide, two-terminal vinyl-phenylmethyl polyfluorene oxide, two-terminal vinyl-diethyl polyfluorene oxide, side chain vinyl-dimethyl poly One or two or more of the group consisting of argon, vinylmethylpolyoxyl, vinyl methoxypolyoxyl, and vinyl resin dispersion. 如申請專利範圍第1或2項所述之無機氧化物粒子與聚矽氧樹脂的複合組成物，其中，前述氫改質聚矽氧係選自由兩末端氫-二甲基聚矽氧、甲基氫-二甲基聚矽氧、甲基氫聚矽氧、乙基氫聚矽氧、甲基氫-苯基甲基聚矽氧、氫化物樹脂所成群組中之1種或2種以上。 The composite composition of the inorganic oxide particles and the polyoxynoxy resin according to claim 1 or 2, wherein the hydrogen-modified polyfluorene oxide is selected from the two-terminal hydrogen-dimethyl polyfluorene, A One or two of a group consisting of hydrogen-dimethyl polyfluorene oxide, methyl hydrogen polyoxynium oxide, ethyl hydrogen polyoxynium oxide, methyl hydrogen-phenylmethyl polyfluorene, and hydride resin the above. 如申請專利範圍第1或2項所述之無機氧化物粒子與聚矽氧樹脂的複合組成物，其中，前述氫改質聚矽氧含有下述式(1)所示之側鏈氫改質聚矽氧： (惟，R1至R8是相互獨立的任意有機基(H除外)，m是1以上之整數，n是包含0的正整數)；前述側鏈氫改質聚矽氧中，m與n之比(m/(m+n))是0.25以上且1以下。 The composite composition of the inorganic oxide particles and the polyoxyxylene resin according to claim 1 or 2, wherein the hydrogen-modified polyfluorene oxygen contains a side chain hydrogen reform represented by the following formula (1). Polyoxane: (However, R 1 to R 8 are independently of each other any organic groups (except H), m is an integer of 1, n is a positive integer including 0); the hydrogen side chain modified poly silicon oxygen, m and n The ratio (m/(m+n)) is 0.25 or more and 1 or less. 一種透明複合體，其係使藉由結合單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物而經表面修飾之無機氧化物粒子以平均分散粒徑為1nm以上且20nm以下之方式分散於聚矽氧樹脂中而成者，同時，在前述聚矽氧樹脂中含有矽氫化反應觸媒。 A transparent composite obtained by combining surface-modified inorganic oxide particles with a polydimethyl methoxy siloxane backbone polymer having one functional group at one end, and having an average dispersed particle diameter of 1 nm or more and 20 nm or less The method is dispersed in a polyoxyxylene resin, and at the same time, the polyfluorene oxide resin contains a hydrazine hydrogenation reaction catalyst. 一種透明複合體，其係在將申請專利範圍第1至5項中任一項所述之無機氧化物粒子與聚矽氧樹脂的複合組 成物成形並固化為預定之形狀，或是在將前述複合組成物固化後予以成形而成者。 A transparent composite which is a composite group of the inorganic oxide particles and the polyoxyxylene resin according to any one of claims 1 to 5. The formed product is formed into a predetermined shape or formed by curing the composite composition. 一種申請專利範圍第1至5項中任一項所述之無機氧化物粒子與聚矽氧樹脂的複合組成物之製造方法，其含有下述步驟：將無機氧化物粒子表面，藉由單邊末端具有1個官能基之聚二甲基矽氧烷骨幹聚合物來修飾，得到經表面修飾的平均分散粒徑為1nm以上且20nm以下之無機氧化物粒子的步驟；以及將前述經表面修飾的平均分散粒徑為1nm以上且20nm以下之無機氧化物粒子、聚矽氧樹脂與反應觸媒混合的步驟。 A method for producing a composite composition of an inorganic oxide particle and a polyoxyxylene resin according to any one of claims 1 to 5, which comprises the step of: surface of the inorganic oxide particle by one side a step of modifying a surface-modified inorganic oxide particle having an average dispersed particle diameter of 1 nm or more and 20 nm or less by modifying a polydimethyl methoxy siloxane backbone polymer having one functional group at the end; and modifying the surface-modified surface described above The step of mixing the inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, and the polyfluorene oxide resin and the reaction catalyst.
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